EP1992659B1 - Molten polyamide moulding composition for manufacturing transparent moulded parts - Google Patents

Molten polyamide moulding composition for manufacturing transparent moulded parts Download PDF

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Publication number
EP1992659B1
EP1992659B1 EP07108313.3A EP07108313A EP1992659B1 EP 1992659 B1 EP1992659 B1 EP 1992659B1 EP 07108313 A EP07108313 A EP 07108313A EP 1992659 B1 EP1992659 B1 EP 1992659B1
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EP
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Prior art keywords
acid
absorber
moulding composition
macmi
transmission
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EP07108313.3A
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German (de)
French (fr)
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EP1992659A1 (en
Inventor
Friedrich Severin Dr. rer. nat. Bühler
Robert Meyer Zu Westram
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EMS Patent AG
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EMS Patent AG
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Priority to EP07108313.3A priority Critical patent/EP1992659B1/en
Priority to JP2008128547A priority patent/JP5241318B2/en
Priority to AU2008202150A priority patent/AU2008202150B2/en
Priority to CN2008102103276A priority patent/CN101328313B/en
Priority to KR1020080045625A priority patent/KR101521298B1/en
Priority to US12/122,468 priority patent/US8138243B2/en
Publication of EP1992659A1 publication Critical patent/EP1992659A1/en
Priority to HK09102269.1A priority patent/HK1122056A1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • C08K5/3475—Five-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the invention relates to a polyamide molding material melt with a UV absorber and a process for the preparation of transparent moldings which have a reduced transmission for light up to a wavelength of 400 nm.
  • UV absorbers for the production of transparent, for light up to a wavelength of 400 nm, a reduced transmission having plastic products, for example, from one of the company HOYA Corp. (Tokyo, Japan) Patents JP 382 44 55 B2 . US Pat. No. 6,441,119 B1 . US 6,673,888 B2 or US Pat. No. 7,009,025 B2 known.
  • the object of these patents is to provide a UV protection which absorbs substantially all UV radiation up to a wavelength of approximately 400 nm. At the same time, the yellow index should be as low as possible.
  • Different monomers diethylene glycol bisallyl carbonate, (thio) urethane, thiirene or episulfide
  • As a UV absorber a dibenzoylmethane compound was used, wherein this UV absorber was added to one of these monomers and this mixture was filled in a mold for casting lenses and polymerized in this form.
  • the object of the present invention is to propose a melt-processable polyamide molding material melt with a UV absorber and a corresponding process for the production of transparent plastic products or molded parts, which have a reduced transmission for light up to a wavelength of 400 nm.
  • a molded part produced with such a polyamide molding material melt has a deep yellow index.
  • a significant reduction of the transmission is preferred, so that a high UV protection results.
  • a polyamide molding compound melt with at least one UV absorber is proposed, which is selected from a group consisting of 1- (4-methoxyphenyl) -3- (4-tert-butylphenyl) propane-1,3-dione and 2- ( 4'-diethylamino-2'-hydroxybenzoyl) benzoic acid n-hexyl ester.
  • This polyamide molding material melt is suitable for the production of transparent plastic products or molded articles which have a reduced transmission for light up to a wavelength of 400 nm.
  • transparent plastic products made of transparent polyamides or their transparent mixtures or transparent blends thereof with one or more semicrystalline polyamides, transparent moldings or transparent films.
  • the light transmission is at least 75%, preferably at least 85%, more preferably at least 90% and most preferably at least 91%, wherein the layer thickness of the measured moldings 2 mm and the layer thickness of the measured films is not more than 800 microns .
  • foils are also referred to as moldings because they are also molded with a device or tool, e.g. a slot die, chill roll. airknife and / or electrospinning.
  • the semicrystalline polyamides preferred for the present invention are selected from the group consisting of PA 6, PA 46, PA 49, PA 410, PA 411, PA 412, PA 413, PA 414, PA 415, PA 416, PA 418, PA 436, PA 66, PA 69, PA 610, PA 611 , PA 612, PA 613, PA 614, PA 615, PA 616, PA 617, PA 618, PA 66/6, PA 6/66/12, PA 6/12, PA 11, PA 12, PA 912, PA 1212 , 6D / 6I, MXD6, MXD6 / MXDI, MXD9, MXD10, MXD11, MXD12, MXD13, MXD14, MXD15, MXD16, MXD17, MXD18, MXD36, PACM9, PACM10, PACM11, PACM12, PACM13, PACM14, PACM15, PACM16, PACM17 , PACM18,
  • the type of transparent molded parts, plastic products or polyamide products is not subject to any restrictions.
  • the transparent polyamide products or molded parts are preferably selected from a group comprising sunlenses, correcting lenses, non-correcting lenses, lenses for spectacles, lenses for optical devices and systems, spectacle parts, goggles, viewing and protective lenses, visors, displays, Watch glasses, instrument housings, lamp covers, filters and foils.
  • the transparent moldings, plastic products or polyamide products consist of at least 50 wt .-% of polyamide, but may also contain layers or admixtures of other plastics or substances, e.g. as a functional or decorative coating.
  • the phosphorus compounds are used in amounts of 0.001 to 0.5 wt .-%, preferably 0.01 to 0.1 wt .-% based on the polyamide.
  • the stabilizers must withstand the thermal stress in a pre-processing compounding or the processing itself, the necessary temperatures for polyamides may be above 350 ° C.
  • UV absorbers in the form of compounds having at least one substituted benzoyl group do not produce any visible deposit formation on surfaces with which the polyamide molding material melts containing these UV absorbers come into contact during production or processing.
  • the inventive polyamide molding material melt in claims 1 and 7 is characterized in that the polyamide molding material melt comprises at least one UV absorber, of which at least one UV absorber is a compound having at least one substituted benzoyl group selected from a A group consisting of 1- (4-methoxyphenyl) -3- (4-tert-butylphenyl) propane-1,3-dione and 2- (4'-diethyl-amino-2'-hydroxybenzoyl) benzoic acid n-hexyl ester, wherein the polyamide molding material melt comprising these at least one UV absorber does not cause visible deposit formation on surfaces with which it comes into contact during processing.
  • at least one UV absorber is a compound having at least one substituted benzoyl group selected from a A group consisting of 1- (4-methoxyphenyl) -3- (4-tert-butylphenyl) propane-1,3-dione and 2- (4'-diethyl-amino-2'-hydroxybenzoyl) be
  • the transparent polyamide products or molded parts according to the invention have a considerably reduced transmission for light with a wavelength of 400 nm or 380 nm, so that a high UV protection results, which is suitable for persons, animals, plants and goods of all kinds to protect against harmful UV radiation.
  • the batch is kept at atmospheric pressure for 0.5 to 1 hour at a temperature of 270 to 350 ° C.
  • the polymer melt is discharged in strand form, cooled in a water bath at 15 to 80 ° C and granulated.
  • the granules are dried for 12 hours at 80 to 120 ° C under nitrogen gas to a water content of less than 0.1 wt .-%.
  • the pressure is regulated to a maximum of 10 bar, preferably to a maximum of 6 bar, both in the receiving vessel and in the reaction vessel.
  • the adjustment of the relative viscosity and thus the molecular weight can be carried out in a manner known per se, e.g. via monofunctional diamines or dicarboxylic acids, or with the aid of difunctional diamines or dicarboxylic acids as chain regulators.
  • the relative viscosity (measured in 0.5% strength by weight m-cresol solution at 20 ° C.) of the transparent polyamides is 1.35-2.15, preferably 1.40-1.90, particularly preferably 1.45-1.85.
  • the glass transition temperature (DSC at a heating rate of 20 ° C./min) of the transparent polyamides is 100-230 ° C., preferably 100-200 ° C., particularly preferably 130-195 ° C.
  • the refractive index n D 20 of the transparent polyamides is 1.49-1.75, preferably 1.49-1.67, more preferably 1.50-1.65, and most preferably 1.51-1.64.
  • the polyamide granules with moisture contents of less than 0.1% by weight are mixed with the pulverulent UV absorbers, an aqueous H 3 PO 2 solution and optionally color pigments for about 30 minutes in a sealed container by means of a so-called tumble mixer.
  • the UV absorbers can also be added in the form of a masterbatch, preferably with a transparent polyamide as the carrier material.
  • the equipment of the polyamide granules with UV absorbers, aqueous H 3 PO 2 solution and optionally color pigments can also be carried out by compounding on a single-shaft or twin-screw extruder with degassing device at set cylinder temperatures of 220 to 350 ° C.
  • the melt is discharged in strand form, cooled in a water bath at 15 to 80 ° C and granulated.
  • the granules are dried for 12 hours at 80 to 120 ° C under nitrogen to a water content of less than 0.1 wt .-%. In this way, by using increased additive concentrations also a masterbatch can be produced.
  • the mixture or the compounded granulate, each with a moisture content of less than 0.1%, can be processed, for example, by means of injection molding, injection-compression molding, closing embossing or expansion embossing, or by extrusion into transparent molded parts or films.
  • the set cylinder temperatures are 220 to 350 ° C
  • the mold temperature is 20 to 140 ° C.
  • the die temperature in the extrusion is 160 to 330 ° C, preferably 240 to 310 ° C.
  • the temperature of the cooling roller in the film extrusion is between 20 ° C and the glass transition temperature (Tg) of the polyamide molding compound to be processed.
  • Table 1 shows the polyamide materials produced at EMS-CHEMIE AG (Domat / Ems, Switzerland): Polyamide material relative viscosity Refractive index n D 20 Glass transition temperature Composition Mol.% MACM12 1.73 1:51 155 - MACMI / MACMT / 12 1:53 1:54 194 38/38/24 6I / 6T / MACMI / MACMT / PACMI / PACMT / 12 1.72 1:59 159 19.25 / 19.25 / 3.75 / 3.75 / 1.35 / 1.35 / 2.7 6I / MXDI 1:48 1.61 150 53.6 / 46.3
  • Table 2 shows the investigated, commercially available UV absorbers by classes and the representatives of each class used: UV absorbers class Manufacturer A Chlorinated 2- (2-hydroxyphenyl) -2H-benzotriazoles Ciba Specialties Chemistry Switzerland AG, B Unchlorinated 2- (2-hydroxyphenyl) -2H-benzotriazoles Cib
  • Test specimens were prepared for testing the UV absorbers in polyamide molding compositions.
  • the preparation of these test specimens in the form of round plates was carried out on an injection molding machine type Krauss-Maffei KM 100-380CX: For this purpose, the mixture or the compounded granules, each with a moisture content of less than 0.1%, placed in the feed hopper of the injection molding machine and in a polished Steel tool with 2 cavities processed to round plates with the dimension 75 x 2 mm.
  • the set cylinder temperatures are between 220 and 350 ° C and the mold temperature at 80 ° C.
  • the injection time varies from 0.5 to 10 s depending on the injected volume.
  • the total cycle time is 20 to 400 s.
  • the round plates were used in the dry state, after having been injection molded for at least 48 hours at room temperature in a dry environment, i. over silica gel.
  • the UV absorber D (Example 11) gave a good result, without the light transmission deteriorated significantly. This was in any case higher than 91%. Likewise a rather good reduction of the transmission of light with a wavelength of 380, 385 and 400 nm was achieved with the UV absorber A (Comparative Example 8). In addition, it was found that the yellow index worsened when irradiating the specimens with sunlight (Suntest). However, even with the untreated test polyamide PA MACM12, the yellow index, ie the yellowing, increased slightly due to exposure to sunlight.
  • the UV absorbers D (Example 16) and E (Example 17) gave a good result without the light transmission deteriorating significantly.
  • a likewise good result resulted from the addition of a mixture of the two UV absorbers D and E (Example 18) to the polyamide molding material melt.
  • the measured light transmission was always higher than 92%.
  • a rather good reduction of the transmission of light with a wavelength of 380, 385 and 400 nm was achieved with the UV absorber A (Comparative Example 15).
  • the UV absorbers D (Example 21) and E (Example 22) gave a good result without the light transmission deteriorating significantly. This was in any case higher than 92%. Likewise, a rather good reduction in the transmission of light having a wavelength of 380, 385 and 400 nm was achieved with a mixture of the two UV absorbers D and E (Example 23) and also with the UV absorber A (Comparative Example 20). In addition, it was found that the yellow index worsened when irradiating the specimens with sunlight (Suntest).
  • the UV absorber C was not approved for the cycle test, because it allows for the test nylon PA 6I / MXDI a significantly higher (worse) transmission of light at all measured wavelengths 380, 385 and 400 nm (see Table 4).
  • the UV absorber D impresses with its physical measurements when it has been incorporated into a polyamide molding material melt. This applies to all test polyamides used PA 6I / MXDI (see Table 4: Example 5), PA MACM12 (see Table 5: Example 11), PA MACMI / MACMT / 12 (see Table 6: Example 16) and PA 6I / 6T / MACMI / MACMT / PACMI / PACMT / 12 (see Table 7: Example 21).
  • This UV absorber D in combination with the test polyamide PA MACM12 (see Table 8: Example 28) causes no visible deposits even after 250 cycles.
  • the UV absorber D thus fulfills all requirements imposed on it and is a UV absorber according to the invention in a polyamide molding material melt.
  • the UV absorber E impresses with the physical measured values when it has been incorporated into a polyamide molding material melt. This applies to all test polyamides PA 6I / MXDI (compare Table 4: Example 6), PA MACMI / MACMT / 12 (see Table 6: Example 17) and PA 6I / 6T / MACMI / MACMT / PACMI / PACMT / 12 (see Table 7: Example 22) in which it was tested.
  • the UV absorber E in combination with the test polyamide PA MACM12 (see Table 8: Example 29) causes no visible deposits even after 250 cycles.
  • the UV absorber E thus fulfills all the requirements placed on it and is a UV absorber according to the invention in a polyamide molding material melt.
  • the combination of the UV absorbers D and E is convincing in the case of the physical measured values when it has been incorporated into a polyamide molding compound melt (compare Examples 23 and 30) and also shows with the test polyamide PA MACM12 (see Table 8: Example 30) 250 cycles no visible deposits.
  • the combination of the UV absorbers D and E thus fulfills all the requirements imposed on them and is a preferred UV absorber combination according to the invention in a polyamide molding material melt.
  • the criterion of the different tendency to form deposits on the surface of the tool is valid, because such a deposit formation significantly affects the quality of the surfaces of the injection molded parts produced with these UV absorbers.
  • the same polyamide molding material melts without these UV absorbers caused no such unwanted deposit formation, so that they must be clearly assigned to the UV absorbers used.
  • the UV masterbatch F (Comparative Example 31) with 8% of the UV absorber A (see Table 3), 5% by weight was added to the test nylon PA MACM12.
  • the proportion of the UV absorber A with respect to the test polyamide is 0.4 wt .-%.
  • the UV absorber A together with the test polyamide PA MACM12 causes visible deposits already after 58 injection cycles.
  • Example 32 Of the UV masterbatch G (Example 32) with 8% of the UV absorber D (see Table 3), 5% by weight was added to the test nylon PA MACM12. Thus, the proportion of UV absorber D with respect to the test polyamide is 0.4% by weight.
  • Table 8 see Example 28
  • the UV absorber D in combination with the test polyamide PA MACM12 causes no visible deposits even after 250 cycles.
  • the two UV absorbers D or E are added to a polyamide molding compound melt, with which transparent plastic products having a reduced transmission for light up to a wavelength of 400 nm are to be produced.
  • the proportion of one of these added UV absorbers is preferably between 0.01 and 1.0 wt .-%, more preferably between 0.05 and 0.4 wt .-%, based on the weight of the polyamide molding composition.
  • the UV absorber E 2- (4'-diethylamino-2'-hydroxybenzoyl) benzoic acid n-hexyl ester, is a representative of Aminohydroxybenzoylbenzoeklareester.
  • the two inventive UV absorbers D and E have as a common chemical feature at least one substituted benzoyl group.
  • Avobenzone also known as dibenzoylmethane or trade names such as Parsol 1789; UV absorber D
  • UV absorber D can degrade under exposure to sunlight (see, eg, US Pat Warwick L. Morison, MD "Photosensitivity” The New England Journal of Medicine. Boston: Mar 11, 2004. Vol. 350, Iss. 11; pg. 1111-1117 ).
  • this degradation can be reduced by admixing the UV absorber B (see Table 5, Examples 12 and 13).
  • UV absorber D Another indication of a possible stabilization of the UV absorber D is shown in the next example.
  • the results obtained are shown below with reference to Table 10 using the test polyamide PA MACM12 used and then explained below: Examples components: unit 34 35 PA MACM12 Wt .-% 99.85 99.85 UV absorber D Wt .-% 12:15 12:15 Makrolex blue RR ppm - 1.4 Testing: Haze % 0.5 0.3 light transmission % 92.0 90.8 YI ASTM D 1925 original 0.8 -3.7 suntest 6.1 4.4 transmission 380 nm,% 0.1 0.0 transmission 385 nm,% 0.3 12:24 transmission 400 nm,% 4.9 4.4
  • polyamide molding compound melts with a UV absorber in the form of a dibenzoylmethane compound D or an aminohydroxybenzoylbenzoic acid ester E on surfaces with which these polyamide molding compound melts came into contact do not cause visible deposit formation.
  • UV absorbers have been found which enable the desired properties in transparent polyamides and which survive both the high temperatures during processing or compounding of the molding compound and the acidic and alkaline end groups of the polyamides. Contrary to expectations caused by the low melting point, UV absorbers of the dibenzoylmethane type do not tend to form visible deposits on plasticizing screws, die lips, tool surfaces or cooling rolls when incorporated into polyamides or when processing dibenzoylmethane-containing polyamide molding compositions. This advantage is retained even when combining the dibenzoylmethanes with unchlorinated hydroxyphenylbenzotriazoles.
  • an embodiment of the novel polyamide molding material melt is furthermore preferred, which is characterized in that it comprises a further UV absorber, which is admixed with the at least one UV absorber D or E.
  • the further UV absorber is selected from a group which is formed from unchlorinated hydroxyphenylbenzotriazoles, aminohydroxybenzoylbenzoic acid esters and dibenzoylmethanes.
  • an unchlorinated hydroxyphenylbenzotriazole in the form of 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol.
  • an aminohydroxybenzoylbenzoic acid ester in the form of 2- (4'-diethylamino-2'-hydroxybenzoyl) benzoic acid n-hexyl ester.
  • Another way to reduce this increase in yellow index is the combination of dibenzoylmethanes, or mixing a compound having at least one substituted benzoyl group, with dyes of the class of anthraquinone dyes, such as Macrolex blue RR or Macrolex red 5B, as example 35 shows.
  • the anthraquinone dyes are used in amounts of 0.1 to 1000 ppm, preferably 0.5 to 500 ppm.
  • a reduction The yellow index also achieve optical brighteners such as Tinopal AMS GX or Tinopal DMS.
  • transparent polyamides which are formed from the aforementioned diamines and dicarboxylic acids and lactams having 4 to 15 carbon atoms and / or ⁇ , ⁇ -amino acids having 4 to 15 carbon atoms.
  • Especially preferred diamines are hexamethylenediamine, trimethylhexamethylenediamine, 2-methyl-1,5-pentanediamine, bis (4-amino-3-methyl-cyclohexyl) methane (MACM for short), bis (4-amino-cyclohexyl) methane (abbreviated PACM), Isophoronediamine, norbornanediamine, m-xylylenediamine and 1,3-bis (aminomethyl) cyclohexane.
  • MAM bis (4-amino-3-methyl-cyclohexyl) methane
  • PACM bis (4-amino-cyclohexyl) methane
  • Isophoronediamine norbornanediamine
  • m-xylylenediamine 1,3-bis (aminomethyl) cyclohexane.
  • dicarboxylic acids are adipic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, brassylic acid, 1,14-tetradecanedioic acid, 1,15-pentadecanoic acid, 1,16-hexadecanedioic acid, 1,18-octadecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, dimer fatty acid having 36 or 44 carbon atoms, isophthalic acid, terephthalic acid and 2,6-naphthalenedicarboxylic acid.
  • lactams are lactams or ⁇ , ⁇ -amino acids having 4, 6, 7, 8, 11 or 12 C atoms. These are the lactams pyrrolidin-2-one (4 C-atoms), ⁇ -caprolactam (6 C-atoms), enanthlactam (7 C-atoms), capryllactam (8 C-atoms), laurolactam (12 C-atoms) resp the ⁇ , ⁇ -amino acids 1,4-aminobutanoic acid, 1,6-aminohexanoic acid, 1,7-aminoheptanoic acid, 1,8-aminooctanoic acid, 1,11-aminoundecanoic acid and 1,12-aminododecanoic acid.
  • PA 6I, PA 6I / 6T, PA 6I / 6T / 6NDC, PA MXDI / 6I, PA MXDI / MXDT / 6I / 6T, PA MXDI / 12I, PA MXDI, with middle and lower ones Refractive indices are PA MACM12, PA MACM13, PA MACM14, PA MACM15, PA MACM16, PA MACM17, PA MACM18, PA 6-3-T, PA MACMI / 12, PA MACM6 / 12, PA MACMT / 12, PA MACMI / MACMNDC, PA MACMT / MACMNDC, PA MACMI / MACM36, PA MACMT / MACM36, PA MACMI / MACMT / 12, PA 6I / MACMI / 12, PA 6I / 6T / MACMI / MACMT, PA 6I / 6T / MACMI / MACMT, PA 6I / 6T /
  • Transparent polyamides may contain one or more additives selected from the group of condensation catalysts, chain regulators, defoamers, stabilizers, lubricants, dyes, flame retardants, photochromic additives, antistatic agents, mold release agents, optical brighteners, natural phyllosilicates, synthetic phyllosilicates.

Description

Die Erfindung betrifft eine Polyamidformmassen-Schmelze mit einem UV-Absorber und ein Verfahren zur Herstellung von transparenten Formteilen, die für Licht bis zu einer Wellenlänge von 400 nm eine reduzierte Transmission aufweisen.The invention relates to a polyamide molding material melt with a UV absorber and a process for the preparation of transparent moldings which have a reduced transmission for light up to a wavelength of 400 nm.

Die Verwendung von UV-Absorbern zur Herstellung von transparenten, für Licht bis zu einer Wellenlänge von 400 nm eine reduzierte Transmission aufweisenden Kunststoff-Produkten ist z.B. aus einem der für die Firma HOYA Corp. (Tokio, Japan) erteilten Patente JP 382 44 55 B2 , US 6,441,119 B1 , US 6,673,888 B2 oder US 7, 009,025 B2 bekannt. Bei diesen Patenten stellte sich die Aufgabe, einen UV-Schutz bereitzustellen, der im wesentlichen alle UV-Strahlung bis zu einer Wellenlänge von ungefähr 400 nm absorbiert. Gleichzeitig sollte der Yellow-Index möglichst niedrig sein. Dabei wurden unterschiedliche Monomere (Diethylenglykol-Bisallyl-Karbonat, (Thio)Urethan, Thiiren oder Episulfid) zum Herstellen von optischen Linsen verwendet. Als UV-Absorber wurde eine Dibenzoylmethan-Verbindung verwendet, wobei dieser UV-Absorber einem dieser Monomere zugemischt und diese Mischung in eine Form zum Giessen von Linsen eingefüllt und in dieser Form polymerisiert wurde.The use of UV absorbers for the production of transparent, for light up to a wavelength of 400 nm, a reduced transmission having plastic products, for example, from one of the company HOYA Corp. (Tokyo, Japan) Patents JP 382 44 55 B2 . US Pat. No. 6,441,119 B1 . US 6,673,888 B2 or US Pat. No. 7,009,025 B2 known. The object of these patents is to provide a UV protection which absorbs substantially all UV radiation up to a wavelength of approximately 400 nm. At the same time, the yellow index should be as low as possible. Different monomers (diethylene glycol bisallyl carbonate, (thio) urethane, thiirene or episulfide) were used to make optical lenses. As a UV absorber, a dibenzoylmethane compound was used, wherein this UV absorber was added to one of these monomers and this mixture was filled in a mold for casting lenses and polymerized in this form.

Die Aufgabe der vorliegenden Erfindung besteht darin, eine thermoplastisch verarbeitbare Polyamidformmassen-Schmelze mit einem UV-Absorber und ein entsprechendes Verfahren zur Herstellung von transparenten Kunststoff-Produkten bzw. Formteilen vorzuschlagen, die für Licht bis zu einer Wellenlänge von 400 nm eine reduzierte Transmission aufweisen. Bevorzugt weist ein mit einer solchen Polyamidformmassen-Schmelze hergestelltes Formteil einen tiefen Yellow-Index auf. Zudem wird eine erhebliche Reduktion der Transmission bevorzugt, so dass ein hoher UV-Schutz resultiert. Diese Aufgabe wird durch die Merkmale der unabhängigen Ansprüche 1 und 7 erfüllt. Dabei wird eine Polyamidformmassen-Schmelze mit zumindest einem UV-Absorber vorgeschlagen, der ausgewählt ist aus einer Gruppe bestehend aus 1-(4-Metoxyphenyl)-3-(4-tert-butylphenyl)propan-1,3-dion und 2-(4'-Diethylamino-2'-hydroxybenzoyl)benzoesäure-n-hexylester. Diese Polyamidformmassen-Schmelze ist zur Herstellung von transparenten Kunststoff-Produkten bzw. Formteilen, die für Licht bis zu einer Wellenlänge von 400 nm eine reduzierte Transmission aufweisen, geeignet.The object of the present invention is to propose a melt-processable polyamide molding material melt with a UV absorber and a corresponding process for the production of transparent plastic products or molded parts, which have a reduced transmission for light up to a wavelength of 400 nm. Preferably, a molded part produced with such a polyamide molding material melt has a deep yellow index. In addition, a significant reduction of the transmission is preferred, so that a high UV protection results. This object is achieved by the features of independent claims 1 and 7. In this case, a polyamide molding compound melt with at least one UV absorber is proposed, which is selected from a group consisting of 1- (4-methoxyphenyl) -3- (4-tert-butylphenyl) propane-1,3-dione and 2- ( 4'-diethylamino-2'-hydroxybenzoyl) benzoic acid n-hexyl ester. This polyamide molding material melt is suitable for the production of transparent plastic products or molded articles which have a reduced transmission for light up to a wavelength of 400 nm.

Im Zusammenhang mit der vorliegenden Erfindung gelten als "transparente Kunststoff-Produkte" aus transparenten Polyamiden oder deren transparenten Mischungen oder deren transparente Blends mit einem oder mehreren teilkristallinen Polyamiden hergestellte, transparente Formteile bzw. transparente Folien. Die Lichttransmission (gemessen nach ASTM 1003) beträgt dabei mindestens 75 %, bevorzugt mindestens 85 %, besonders bevorzugt mindestens 90 % und ganz besonders bevorzugt mindestens 91 %, wobei die Schichtdicke der gemessenen Formteile 2 mm und die Schichtdicke der gemessenen Folien maximal 800 µm beträgt. Allgemein werden im Zusammenhang mit dieser Erfindung Folien auch als Formteile bezeichnet, weil diese ebenfalls mit einer Vorrichtung oder einem Werkzeug, z.B. einer Breitschlitzdüse, Kühlwalze. einem Airknife und/oder Elektrospinning, in ihre Form gebracht werden.In connection with the present invention, "transparent plastic products" made of transparent polyamides or their transparent mixtures or transparent blends thereof with one or more semicrystalline polyamides, transparent moldings or transparent films. The light transmission (measured according to ASTM 1003) is at least 75%, preferably at least 85%, more preferably at least 90% and most preferably at least 91%, wherein the layer thickness of the measured moldings 2 mm and the layer thickness of the measured films is not more than 800 microns , Generally, in the context of this invention, foils are also referred to as moldings because they are also molded with a device or tool, e.g. a slot die, chill roll. airknife and / or electrospinning.

Die für die vorliegende Erfindung bevorzugten, teilkristallinen Polyamide sind ausgewählt aus der Gruppe PA 6, PA46, PA49, PA410, PA411, PA412, PA413, PA414, PA415, PA416, PA418, PA436, PA 66, PA 69, PA 610, PA 611, PA 612, PA 613, PA 614, PA 615, PA 616, PA 617, PA 618, PA 66/6, PA 6/66/12, PA 6/12, PA 11, PA 12, PA 912, PA 1212, 6T/6I, MXD6, MXD6/MXDI, MXD9, MXD10, MXD11, MXD12, MXD13, MXD14, MXD15, MXD16, MXD17, MXD18, MXD36, PACM9, PACM10, PACM11, PACM12, PACM13, PACM14, PACM15, PACM16, PACM17, PACM18, PACM36, Polyetheramiden, Polyetheresteramiden und Polyesteramiden oder deren Mischungen oder Copolymeren. Besonders bevorzugt sind dabei teilkristalline Polyamide aus der Gruppe PA 6, PA 612, PA 614, PA 6/66/12, PA 6/12, PA 11, PA 12, Polyetheramide und Polyetheresteramide.The semicrystalline polyamides preferred for the present invention are selected from the group consisting of PA 6, PA 46, PA 49, PA 410, PA 411, PA 412, PA 413, PA 414, PA 415, PA 416, PA 418, PA 436, PA 66, PA 69, PA 610, PA 611 , PA 612, PA 613, PA 614, PA 615, PA 616, PA 617, PA 618, PA 66/6, PA 6/66/12, PA 6/12, PA 11, PA 12, PA 912, PA 1212 , 6D / 6I, MXD6, MXD6 / MXDI, MXD9, MXD10, MXD11, MXD12, MXD13, MXD14, MXD15, MXD16, MXD17, MXD18, MXD36, PACM9, PACM10, PACM11, PACM12, PACM13, PACM14, PACM15, PACM16, PACM17 , PACM18, PACM36, polyetheramides, polyetheresteramides and polyesteramides or mixtures or copolymers thereof. Particularly preferred are partially crystalline Polyamides from the group PA 6, PA 612, PA 614, PA 6/66/12, PA 6/12, PA 11, PA 12, polyetheramides and polyetheresteramides.

Die Art der transparenten Formteile, Kunstoff-Produkte bzw. Polyamid-Produkte unterliegt keinerlei Beschränkungen. Bevorzugt sind die transparenten Polyamid-Produkte bzw. Formteile ausgewählt aus einer Gruppe, die Sonnenlinsen, korrigierende Linsen, nicht-korrigierende Linsen, Linsen für Brillen, Linsen für optische Geräte und Systeme, Brillenteile, Schutzbrillen, Sicht- und Schutzscheiben, Visiere, Displays, Uhrengläser, Gerätegehäuse, Lampenabdeckungen, Filter und Folien umfasst.The type of transparent molded parts, plastic products or polyamide products is not subject to any restrictions. The transparent polyamide products or molded parts are preferably selected from a group comprising sunlenses, correcting lenses, non-correcting lenses, lenses for spectacles, lenses for optical devices and systems, spectacle parts, goggles, viewing and protective lenses, visors, displays, Watch glasses, instrument housings, lamp covers, filters and foils.

Die transparenten Formteile, Kunststoff-Produkte bzw. Polyamid-Produkte bestehen zu mindestens 50 Gew.-% aus Polyamid, können aber auch Schichten oder Zumischungen anderer Kunststoffe oder Stoffe enthalten, z.B. als funktionelle oder dekorative Beschichtung.The transparent moldings, plastic products or polyamide products consist of at least 50 wt .-% of polyamide, but may also contain layers or admixtures of other plastics or substances, e.g. as a functional or decorative coating.

Beim Testen von transparenten Polyamiden mit kommerziell erhältlichen UV-Absorbern stellte sich allerdings heraus, dass die heute weit verbreiteten halogenierten Hydroxyphenylbenztriazole einen starken Gelbstich erzeugen. Der Yellow-Index (Gelbstich) durch die Zugabe von UV-Stabilisatoren nimmt insbesondere dann stark zu, wenn z.B. Linsen im Spritzgussverfahren hergestellt werden. Die hohen Verarbeitungstemperaturen für Polyamide und die sauren und alkalischen Endgruppen dieser Polymeren erschweren das Einstellen einer geringen Verfärbung. Üblicherweise wird deshalb ein Polyamid, das bei der Verarbeitung zur Verfärbung neigt, selbst mit Phosphor Verbindungen, z.B. mit phosphorhaltigen Säuren, wie H3PO2, H3PO3, H3PO4 oder deren Salzen geschützt, welche die verwendeten UV-Stabilisatoren nicht angreifen sollen. Die Phosphorverbindungen werden in Mengen von 0,001 bis 0.5 Gew.-%, bevorzugt 0.01 bis 0.1 Gew.-% bezogen auf das Polyamid verwendet. Zur Einarbeitung des UV-Schutzes in die Polyamidformmassen-Schmelze müssen die Stabilisatoren die thermische Belastung bei einer der Verarbeitung vorausgehenden Compoundierung bzw. der Verarbeitung selbst überstehen, wobei die dazu notwendigen Temperaturen bei Polyamiden über 350 °C betragen können.When testing transparent polyamides with commercially available UV absorbers, however, it turned out that the halogenated hydroxyphenylbenzotriazoles widespread today produce a strong yellowish tinge. The yellow index (yellowness) due to the addition of UV stabilizers increases particularly when, for example, lenses are produced by injection molding. The high processing temperatures for polyamides and the acidic and alkaline end groups of these polymers make it difficult to set a slight discoloration. Usually, therefore, a polyamide which tends to discolor during processing is itself protected with phosphorus compounds, eg phosphorus-containing acids such as H 3 PO 2 , H 3 PO 3 , H 3 PO 4 or salts thereof, which do not use the UV stabilizers used to attack. The phosphorus compounds are used in amounts of 0.001 to 0.5 wt .-%, preferably 0.01 to 0.1 wt .-% based on the polyamide. For incorporation of the UV protection in the polyamide molding material melt, the stabilizers must withstand the thermal stress in a pre-processing compounding or the processing itself, the necessary temperatures for polyamides may be above 350 ° C.

Beim Testen von transparenten Polyamiden mit kommerziell erhältlichen UV-Absorbern stellte sich zudem heraus, dass die Verarbeitung von Polyamidformmassen, welche halogenierte Hydroxyphenylbenztriazole enthalten, zur Bildung von Ablagerungen in der Plastifiziereinheit bzw. auf der Werkzeugoberfläche führt. Diese Ablagerungen können die Oberflächenqualität der Polyamidformkörper erheblich beeinträchtigen und müssen regelmässig manuell entfernt werden, was jeweils zur Unterbrechung des Produktionsprozesses führt.When testing transparent polyamides with commercially available UV absorbers, it has also been found that the processing of polyamide molding compositions containing halogenated hydroxyphenylbenzotriazoles leads to the formation of deposits in the plasticizing unit or on the tool surface. These deposits can significantly affect the surface quality of the polyamide moldings and must be regularly removed manually, which in each case leads to the interruption of the production process.

Überraschenderweise konnte festgestellt werden, dass UV-Absorber in Form von Verbindungen die mindestens eine substituierte Benzoylgruppe aufweisen, keine sichtbaren Belagsbildungen auf Oberflächen erzeugen, mit denen die diesen UV-Absorber enthaltenden Polyamidformmassen-Schmelzen während der Herstellung oder der Verarbeitung in Kontakt kommen.It has surprisingly been found that UV absorbers in the form of compounds having at least one substituted benzoyl group do not produce any visible deposit formation on surfaces with which the polyamide molding material melts containing these UV absorbers come into contact during production or processing.

Aus diesen Gründen ist die erfindungsgemässe Polyamidformmassen-Schmelze in den Ansprüchen 1 und 7 dadurch gekennzeichnet, dass die Polyamidformmassen-Schmelze mindestens einen UV-Absorber umfasst, wovon zumindest ein UV-Absorber eine Verbindung ist, die mindestens eine substituierte Benzoylgruppe aufweist, ausgewählt aus einer Gruppe bestehend aus 1-(4-Metoxyphenyl)-3-(4-tert-butylphenyl)propan-1,3-dion und 2-(4'-Diethyl-amino-2'-hydroxybenzoyl) benzoesäure-n-hexylester, wobei die diesen zumindest einen UV-Absorber umfassende Polyamidformmassen-Schmelze auf Oberflächen, mit denen sie während der Verarbeitung in Kontakt kommt, keine sichtbare Belagsbildung verursacht.For these reasons, the inventive polyamide molding material melt in claims 1 and 7 is characterized in that the polyamide molding material melt comprises at least one UV absorber, of which at least one UV absorber is a compound having at least one substituted benzoyl group selected from a A group consisting of 1- (4-methoxyphenyl) -3- (4-tert-butylphenyl) propane-1,3-dione and 2- (4'-diethyl-amino-2'-hydroxybenzoyl) benzoic acid n-hexyl ester, wherein the polyamide molding material melt comprising these at least one UV absorber does not cause visible deposit formation on surfaces with which it comes into contact during processing.

Die erfindungsgemässen transparenten Polyamid-Produkte bzw. Formteile weisen eine erheblich reduzierte Transmission für Licht mit einer Wellenlänge von 400 nm bzw. von 380 nm auf, so dass ein hoher UV-Schutz resultiert, der dazu geeignet ist, Personen, Tiere, Pflanzen und Güter aller Art vor schädlicher UV-Strahlung zu schützen.The transparent polyamide products or molded parts according to the invention have a considerably reduced transmission for light with a wavelength of 400 nm or 380 nm, so that a high UV protection results, which is suitable for persons, animals, plants and goods of all kinds to protect against harmful UV radiation.

Zusätzliche bevorzugte Weiterbildungen der erfindungsgemässen Polyamidformmassen-Schmelze und weitere erfinderische Merkmale ergeben sich aus den weiteren Ansprüchen.Additional preferred developments of the novel polyamide molding compound melt and further inventive features emerge from the further claims.

Die Herstellung der transparenten Polyamide erfolgte in an sich bekannter Weise und in bekannten, rührbaren Druckautoklaven mit einem Vorlagegefäss und einem Reaktionsgefäss:

  • Im Vorlagegefäss wird deionisiertes Wasser vorgelegt und die Monomere und Additive zugegeben. Danach wird mehrfach mit Stickstoffgas inertisiert. Unter Rühren wird auf 180 bis 230 °C unter dem sich einstellenden Druck aufgeheizt, um eine homogene Lösung zu erhalten. Diese Lösung wird durch ein Sieb in das Reaktionsgefäss gepumpt und dort auf die gewünschte Reaktionstemperatur von 270 bis 350 °C bei einem Druck von maximal 30 bar aufgeheizt. Der Ansatz wird in der Druckphase für 2 bis 4 Stunden auf der Reaktionstemperatur gehalten. In der anschliessenden Entspannungsphase wird der Druck innerhalb von 1 bis 2 Stunden auf atmosphärischen Druck reduziert, wobei die Temperatur leicht sinken kann.
The preparation of the transparent polyamides was carried out in a manner known per se and in known, stirrable pressure autoclaves with a receiver vessel and a reaction vessel:
  • Deionized water is introduced into the receiver and the monomers and additives are added. Thereafter, it is repeatedly inertized with nitrogen gas. With stirring is heated to 180 to 230 ° C under autogenous pressure to obtain a homogeneous solution. This solution is pumped through a sieve into the reaction vessel and there heated to the desired reaction temperature of 270 to 350 ° C at a pressure of 30 bar maximum. The batch is kept in the pressure phase for 2 to 4 hours at the reaction temperature. In the subsequent relaxation phase, the pressure is reduced to atmospheric pressure within 1 to 2 hours, during which the temperature can drop slightly.

In der folgenden Entgasungsphase wird der Ansatz bei atmosphärischem Druck für 0.5 bis 1 Stunden auf einer Temperatur von 270 bis 350 °C gehalten. Die Polymerschmelze wird in Strangform ausgetragen, im Wasserbad bei 15 bis 80 °C abgekühlt und granuliert. Das Granulat wird für 12 Stunden bei 80 bis 120 °C unter Stickstoffgas auf einen Wassergehalt von weniger als 0.1 Gew.-% getrocknet.In the following degassing phase, the batch is kept at atmospheric pressure for 0.5 to 1 hour at a temperature of 270 to 350 ° C. The polymer melt is discharged in strand form, cooled in a water bath at 15 to 80 ° C and granulated. The granules are dried for 12 hours at 80 to 120 ° C under nitrogen gas to a water content of less than 0.1 wt .-%.

Sollte als Monomer Xylylendiamin verwendet werden, wird sowohl im Vorlagegefäss als auch im Reaktionsgefäss der Druck auf maximal 10 bar, bevorzugt auf maximal 6 bar geregelt.If xylylenediamine is used as the monomer, the pressure is regulated to a maximum of 10 bar, preferably to a maximum of 6 bar, both in the receiving vessel and in the reaction vessel.

Die Einstellung der relativen Viskosität und damit der Molmasse kann in an sich bekannter Weise, z.B. über monofunktionelle Diamine oder Dicarbonsäuren, oder mit Hilfe von difunktionellen Diaminen oder Dicarbonsäuren als Kettenregler erfolgen.The adjustment of the relative viscosity and thus the molecular weight can be carried out in a manner known per se, e.g. via monofunctional diamines or dicarboxylic acids, or with the aid of difunctional diamines or dicarboxylic acids as chain regulators.

Die relative Viskosität (gemessen in 0.5 Gew.-%-iger m-Kresollösung bei 20 °C) der transparenten Polyamide beträgt 1.35 - 2.15, bevorzugt 1.40 - 1.90, besonders bevorzugt 1.45 - 1.85.The relative viscosity (measured in 0.5% strength by weight m-cresol solution at 20 ° C.) of the transparent polyamides is 1.35-2.15, preferably 1.40-1.90, particularly preferably 1.45-1.85.

Die Glasübergangstemperatur (DSC mit einer Aufheizrate von 20 °C/min) der transparenten Polyamide beträgt 100 - 230 °C, bevorzugt 100 - 200 °C, besonders bevorzugt 130 - 195 °C.The glass transition temperature (DSC at a heating rate of 20 ° C./min) of the transparent polyamides is 100-230 ° C., preferably 100-200 ° C., particularly preferably 130-195 ° C.

Der Brechungsindex nD 20 der transparenten Polyamide beträgt 1.49 - 1.75, bevorzugt 1.49 - 1.67, besonders bevorzugt 1.50 - 1.65 und ganz besonders bevorzugt 1.51 - 1.64.The refractive index n D 20 of the transparent polyamides is 1.49-1.75, preferably 1.49-1.67, more preferably 1.50-1.65, and most preferably 1.51-1.64.

Das Polyamidgranulat mit Feuchten von weniger als 0.1 Gew.-% wird mit den pulverförmigen UV-Absorbern, einer wässrigen H3PO2 Lösung und gegebenenfalls Farbpigmenten ca. 30 Minuten in einem verschlossenen Behälter mittels eines sogenannten Taumelmischers gemischt. Die UV-Absorber können dabei auch in Form eines Masterbatches, bevorzugt mit einem transparenten Polyamid als Trägermaterial, zugegeben werden.The polyamide granules with moisture contents of less than 0.1% by weight are mixed with the pulverulent UV absorbers, an aqueous H 3 PO 2 solution and optionally color pigments for about 30 minutes in a sealed container by means of a so-called tumble mixer. The UV absorbers can also be added in the form of a masterbatch, preferably with a transparent polyamide as the carrier material.

Die Ausrüstung des Polyamidgranulats mit UV-Absorbern, wässriger H3PO2 Lösung und gegebenenfalls Farbpigmenten kann auch mittels einer Compoundierung auf einem Einwellen- oder Doppelwellen-Extruder mit Entgasungsvorrichtung bei eingestellten Zylindertemperaturen von 220 bis 350 °C erfolgen. Die Schmelze wird in Strangform ausgetragen, im Wasserbad bei 15 bis 80 °C abgekühlt und granuliert. Das Granulat wird für 12 Stunden bei 80 bis 120 °C unter Stickstoff auf einen Wassergehalt von weniger als 0.1 Gew.-% getrocknet. Auf diese Weise lässt sich durch Verwendung erhöhter Additivkonzentrationen auch ein Masterbatch herstellen.The equipment of the polyamide granules with UV absorbers, aqueous H 3 PO 2 solution and optionally color pigments can also be carried out by compounding on a single-shaft or twin-screw extruder with degassing device at set cylinder temperatures of 220 to 350 ° C. The melt is discharged in strand form, cooled in a water bath at 15 to 80 ° C and granulated. The granules are dried for 12 hours at 80 to 120 ° C under nitrogen to a water content of less than 0.1 wt .-%. In this way, by using increased additive concentrations also a masterbatch can be produced.

Die Mischung oder das compoundierte Granulat, jeweils mit Feuchten von weniger als 0.1 %, kann beispielsweise über Spritzguss, Spritzprägen, Schliessprägen bzw. Expansionsprägen, oder über Extrusion zu transparenten Formteilen bzw. Folien verarbeitet werden. Die eingestellten Zylindertemperaturen betragen dabei 220 bis 350 °C, die Werkzeugtemperatur liegt bei 20 bis 140 °C. Die Düsentemperatur bei der Extrusion beträgt 160 bis 330 °C, bevorzugt 240 bis 310 °C. Die Temperatur der Kühlwalze bei der Folienextrusion liegt zwischen 20 °C und der Glasübergangstemperatur (Tg) der zu verarbeitenden Polyamidformmasse.
Die Tabelle 1 zeigt die verwendeten, bei der EMS-CHEMIE AG (Domat/Ems, Schweiz) hergestellten Polyamidmaterialien: Polyamid-Material relative Viskosität Brechungsindex nD 20 Glasübergangstemperatur Zusammensetzung Mol.-% MACM12 1.73 1.51 155 - MACMI/MACMT/12 1.53 1.54 194 38/38/24 6I/6T/MACMI/MACMT/ PACMI/PACMT/12 1.72 1.59 159 19.25/19.25/3.75/3.75/1.35/1.35/2.7 6I/MXDI 1.48 1.61 150 53.6/46.3
Die Tabelle 2 zeigt die untersuchten, kommerziell erhältlichen UV-Absorber nach Klassen und den jeweils verwendeten Vertreter einer Klasse: UV-Absorber Klasse Hersteller A Chlorierte 2-(2-Hydroxyphenyl)-2H-benzotriazole Ciba Spezalitätenchemie Schweiz AG, B Unchlorierte 2-(2-Hydroxyphenyl)-2H-benzotriazole Ciba Spezalitätenchemie Schweiz AG, C (2-Hydroxyphenyl)-s-triazine Ciba Spezalitätenchemie Schweiz AG, D Dibenzoylmethane DSM, Niederlande E Aminohydroxybenzoylbenzoesäureester BASF AG, Deutschland UV-Absorber Verwendeter Vertreter Handelsnamen Schmelzpunkt [°C] A 2-(5-Chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)phenol Tinuvin 326 138 B 2-(2H-Benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol Tinuvin 234 139 C 2,4-Diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-s-trianzin Tinuvin 1577 149 D 1-(4-Metoxyphenyl)-3-(4-tert-butylphenyl)propan-1,3-dion Parsol 1789 82 E 2-(4'-Diethylamino-2'-hydroxybenzoyl)benzoesäure-n-hexylester Uvinul A Plus 54
Die Tabelle 3 zeigt die hergestellten Masterbatches: Masterbatch Zusammensetzung Hersteller Trägermaterial Gew.-% UV-Absorber Gew.-% F PA MACM12 92 A 8 EMS-CHEMIE AG, Schweiz G PA MACM12 92 D 8 EMS-CHEMIE AG, Schweiz H PA MACM12 92 D 7 EMS-CHEMIE AG, Schweiz B 1 The mixture or the compounded granulate, each with a moisture content of less than 0.1%, can be processed, for example, by means of injection molding, injection-compression molding, closing embossing or expansion embossing, or by extrusion into transparent molded parts or films. The set cylinder temperatures are 220 to 350 ° C, the mold temperature is 20 to 140 ° C. The die temperature in the extrusion is 160 to 330 ° C, preferably 240 to 310 ° C. The temperature of the cooling roller in the film extrusion is between 20 ° C and the glass transition temperature (Tg) of the polyamide molding compound to be processed.
Table 1 shows the polyamide materials produced at EMS-CHEMIE AG (Domat / Ems, Switzerland): Polyamide material relative viscosity Refractive index n D 20 Glass transition temperature Composition Mol.% MACM12 1.73 1:51 155 - MACMI / MACMT / 12 1:53 1:54 194 38/38/24 6I / 6T / MACMI / MACMT / PACMI / PACMT / 12 1.72 1:59 159 19.25 / 19.25 / 3.75 / 3.75 / 1.35 / 1.35 / 2.7 6I / MXDI 1:48 1.61 150 53.6 / 46.3
Table 2 shows the investigated, commercially available UV absorbers by classes and the representatives of each class used: UV absorbers class Manufacturer A Chlorinated 2- (2-hydroxyphenyl) -2H-benzotriazoles Ciba Specialties Chemistry Switzerland AG, B Unchlorinated 2- (2-hydroxyphenyl) -2H-benzotriazoles Ciba Specialties Chemistry Switzerland AG, C (2-hydroxyphenyl) -s-triazines Ciba Specialties Chemistry Switzerland AG, D dibenzoylmethanes DSM, Netherlands e Aminohydroxybenzoylbenzoesäureester BASF AG, Germany UV absorbers Used representative trade names Melting point [° C] A phenol 2- (5-chloro-2H-benzotriazol-2-yl) -6- (1,1-dimethylethyl) Tinuvin 326 138 B 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol Tinuvin 234 139 C 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -s-triazine Tinuvin 1577 149 D 1- (4-methoxyphenyl) -3- (4-tert-butylphenyl) propane-1,3-dione Parsol 1789 82 e 2- (4'-diethylamino-2'-hydroxybenzoyl) benzoic acid n-hexyl ester Uvinul A Plus 54
Table 3 shows the masterbatches produced: masterbatch composition Manufacturer support material Wt .-% UV absorbers Wt .-% F PA MACM12 92 A 8th EMS-CHEMIE AG, Switzerland G PA MACM12 92 D 8th EMS-CHEMIE AG, Switzerland H PA MACM12 92 D 7 EMS-CHEMIE AG, Switzerland B 1

Zum Testen der UV-Absorber in Polyamidformmassen wurden Prüfkörper hergestellt. Die Herstellung dieser Prüfkörper in Form von Rundplatten erfolgte auf einer Spritzgussmaschine Typ Krauss-Maffei KM 100-380CX: Dazu wird die Mischung oder das compoundierte Granulat, jeweils mit einer Feuchte von weniger als 0.1 %, in den Einzugstrichter der Spritzgussmaschine gegeben und in einem polierten Stahlwerkzeug mit 2 Kavitäten zu Rundplatten mit der Dimension 75 x 2 mm verarbeitet. Die eingestellten Zylindertemperaturen liegen dabei zwischen 220 und 350 °C und die Werkzeugtemperatur bei 80 °C. Die Einspritzzeit bewegt sich je nach eingespritztem Volumen von 0.5 bis 10 s. Die gesamte Zykluszeit beträgt 20 bis 400 s. Die Rundplatten wurden im trockenen Zustand verwendet, nachdem sie nach dem Spritzguss mindestens 48 h bei Raumtemperatur in trockener Umgebung, d.h. über Silicagel, gelagert wurden.Test specimens were prepared for testing the UV absorbers in polyamide molding compositions. The preparation of these test specimens in the form of round plates was carried out on an injection molding machine type Krauss-Maffei KM 100-380CX: For this purpose, the mixture or the compounded granules, each with a moisture content of less than 0.1%, placed in the feed hopper of the injection molding machine and in a polished Steel tool with 2 cavities processed to round plates with the dimension 75 x 2 mm. The set cylinder temperatures are between 220 and 350 ° C and the mold temperature at 80 ° C. The injection time varies from 0.5 to 10 s depending on the injected volume. The total cycle time is 20 to 400 s. The round plates were used in the dry state, after having been injection molded for at least 48 hours at room temperature in a dry environment, i. over silica gel.

Die Prüfkörper in der Form der Rundplatten wurden nach folgenden Normen getestet und vermessen:

  • Relative Viskosität:
    • ISO 307
    • 0,5 Gew.-%-ige m-Kresollösung
    • Temperatur 20 °C
    • Berechnung der relativen Viskosität (RV) nach RV = t/t0 in Anlehnung an Abschnitt 11 der Norm.
  • Glasumwandlungstemperatur (Tg)
    • ISO-Norm 11357-1/-2
    • Granulat
    • Die Differential Scanning Calorimetry (DSC) wurde mit Aufheizrate von 20 °C/min durchgeführt. Angegeben wird die Temperatur für den Onset.
  • Lichttransmission und Haze:
    • ASTM D 1003
    • Rundplatte, Dicke 2 mm, Radius 37,5 mm
    • Temperatur 23 °C
The test specimens in the form of round plates were tested and measured according to the following standards:
  • Relative viscosity:
    • ISO 307
    • 0.5% by weight m-cresol solution
    • Temperature 20 ° C
    • Calculation of the relative viscosity (RV) according to RV = t / t 0 on the basis of section 11 of the standard.
  • Glass transition temperature (Tg)
    • ISO standard 11357-1 / -2
    • granules
    • The differential scanning calorimetry (DSC) was carried out at a heating rate of 20 ° C / min. Indicated is the temperature for the onset.
  • Light transmission and Haze:
    • ASTM D 1003
    • Round plate, thickness 2 mm, radius 37.5 mm
    • Temperature 23 ° C

Messgerät Haze Gard plus der Firma Byk Gardner mit CIE Lichtart C. Der Lichttransmissions- und der Hazewert werden in % der eingestrahlten Lichtmenge angegeben.
Transmission bei einer definierten Wellenlänge
Rundplatte, Dicke 2 mm, Radius 37,5 mm
Temperatur 23 °CHaze Gard plus meter from Byk Gardner with CIE light C. The light transmission and haze values are given in% of the incident light quantity.
Transmission at a defined wavelength
Round plate, thickness 2 mm, radius 37.5 mm
Temperature 23 ° C

Die Transmission wird mit dem UV-VIS-Spektrometer Lambda 35 der Firma Perkin-Elmer bei den einzelnen Wellenlängen 380, 385, 400 nm nach der Gleichung T = I / I o × 100

Figure imgb0001
ermittelt, wobei Io die Intensität des eingestrahlten Lichts und I die Intensität des durchgetretenen Lichts darstellt.The transmission is measured with the UV-VIS spectrometer Lambda 35 from Perkin-Elmer at the individual wavelengths 380, 385, 400 nm according to the equation T = I / I O × 100
Figure imgb0001
 where I o is the intensity of the incident light and I is the intensity of the transmitted light.

Bei Lambda 35 handelt es sich um ein Zweistrahlgerät mit einer Wellenlängenauflösung von 0.5 nm und einem Wellenlängenbereich von 190 nm bis 1100 nm.

  • Yellow Index
    ASTM D 1925
    Rundplatte, Dicke 2 mm, Radius 37,5 mm
    Temperatur 23 °C
  • Brechungsindex (Brechzahl)
    DIN 53491
    Rundplatte, Dicke 2 mm, Radius 37,5 mm
    Temperatur 20 °C
    Brechungsindex nD 20: Messung bei der Standardwellenlänge - der gelben D-Linie des Natriums - bei 20 °C.
Lambda 35 is a two-beam device with a wavelength resolution of 0.5 nm and a wavelength range of 190 nm to 1100 nm.
  • Yellow index
    ASTM D 1925
    Round plate, thickness 2 mm, radius 37.5 mm
    Temperature 23 ° C
  • Refractive index (refractive index)
    DIN 53491
    Round plate, thickness 2 mm, radius 37.5 mm
    Temperature 20 ° C
    Refractive index n D 20 : Measurement at the standard wavelength - the yellow D-line of sodium - at 20 ° C.

An Hand der eingangs formulierten Aufgabenstellung wurde eine Reihe von Bedingungen zusammengestellt, welche eine erfindungsgemässe Polyamidformmassen-Schmelze erfüllen soll:

  • Es soll ein UV-Schutz bereit gestellt werden, der UV-Strahlung unterhalb einer Wellenlänge von 400 nm, 385 nm oder 380 nm absorbiert, so dass die Transmission dieser Formteile bei einer Formteildicke von 2 mm für Licht mit einer Wellenlänge von 400 nm weniger als 20 %, bevorzugt weniger als 10 % und speziell bevorzugt weniger als 5 % und besonders bevorzugt weniger als 1 % beträgt.
  • Der Yellow-Index (YI), gemessen nach ASTM D 1925 an 2 mm dicken Platten, soll im Originalzustand niedrig sein und den Wert 5, bevorzugt den Wert 2, nicht übersteigen.
  • Es sollen möglichst wenig Ablagerungen bzw. Belagsbildungen bei der Verarbeitung entstehen. Als Test wurde die Belagsbildung in einer Spritzgussform ausgewählt, wobei die Resultate prinzipiell auch auf Kühlwalzen zur Herstellung von Folien übertragen werden können.
On the basis of the task formulated at the outset, a number of conditions have been put together which are intended to fulfill a polyamide molding material melt according to the invention:
  • It is intended to provide a UV protection that absorbs UV radiation below a wavelength of 400 nm, 385 nm or 380 nm, so that the transmission of these moldings with a molded part thickness of 2 mm for light with a wavelength of 400 nm less than 20%, preferably less than 10%, and more preferably less than 5% and most preferably less than 1%.
  • The yellow index (YI), measured according to ASTM D 1925 on 2 mm thick plates, should be low in the original state and should not exceed the value 5, preferably the value 2.
  • It should arise as little as possible deposits or deposits during processing. As a test, the deposit formation was selected in an injection mold, wherein the results can in principle be transferred to chill rolls for the production of films.

Im folgenden werden an Hand der Tabelle 4 die erhaltenen Resultate an Hand des verwendeten Testpolyamids PA 6I/MXDI gezeigt und anschliessend erläutert: Vergleichsbeispiele Beispiele Komponenten: Einheit 1 2 3 4 5 6 PA 6I/MXDI Gew.-% 100.0 99.9 99.9 99.9 99.9 99.9 UV-Absorber A Gew.-% - 0.1 - - - - UV-Absorber B Gew.-% - - 0.1 - - - UV-Absorber C Gew.-% - - - 0.1 - - UV-Absorber D Gew.-% - - - - 0.1 - UV-Absorber E Gew.-% - - - - - 0.1 Tests: Haze % 0.4 0.6 0.7 0.7 0.5 0.6 Lichttransmission % 92.1 91.6 91.4 91.6 91.8 91.4 YI ASTM D 1925 original 2.3 3.1 7.2 2.9 4.9 4.9 Suntest 26.0 7.5 10.1 8.0 13.3 11.4 Transmission 380 nm, % 63.0 0.0 0.0 6.5 0.0 0.0 Transmission 385 nm, % 67.3 0.3 0.3 18.3 0.2 0.2 Transmission 400 nm, % 74.9 9.9 10.6 57.5 3.7 7.4 Verglichen mit dem unbehandelten Testpolyamid PA 6I/MXDI (Vergleichsbeispiel 1), reduziert die Zugabe von 0.1 Gew.-% eines UV-Absorbers zum Testpolyamid in jedem Fall die Transmission von Licht mit einer Wellenlänge von 380, 385 und 400 nm, die am Prüfkörper gemessen wurde. Dabei ergaben die beiden UV-Absorber D (Beispiel 5) und E (Beispiel 6) die besten Resultate, ohne dass sich die Lichttransmission erheblich verschlechterte. Diese war in jedem Fall höher als 91 %. Ebenfalls eine recht gute Reduktion der Transmission von Licht mit einer Wellenlänge von 380, 385 und 400 nm wurde mit den UV-Absorbern A (Vergleichsbeispiel 2) und B (Vergleichsbeispiel 3) erreicht. Zudem zeigte sich, dass sich der Yellow-Index beim Bestrahlen der Prüfkörper mit Sonnenlicht (Suntest) verschlechterte. Allerdings stieg auch beim unbehandelten Testpolyamid PA 6I/MXDI der Yellow-Index, also die Vergilbung, durch die Bestrahlung mit Sonnenlicht an. Der Haze-Wert war in allen Fällen in Ordnung.The results obtained are shown below with reference to Table 4 using the test polyamide PA 6I / MXDI used and then explained below: Comparative Examples Examples components: unit 1 2 3 4 5 6 PA 6I / MXDI Wt .-% 100.0 99.9 99.9 99.9 99.9 99.9 UV absorber A Wt .-% - 0.1 - - - - UV absorber B Wt .-% - - 0.1 - - - UV absorber C Wt .-% - - - 0.1 - - UV absorber D Wt .-% - - - - 0.1 - UV absorber E Wt .-% - - - - - 0.1 Testing: Haze % 0.4 0.6 0.7 0.7 0.5 0.6 light transmission % 92.1 91.6 91.4 91.6 91.8 91.4 YI ASTM D 1925 original 2.3 3.1 7.2 2.9 4.9 4.9 suntest 26.0 7.5 10.1 8.0 13.3 11.4 transmission 380 nm,% 63.0 0.0 0.0 6.5 0.0 0.0 transmission 385 nm,% 67.3 0.3 0.3 18.3 0.2 0.2 transmission 400 nm,% 74.9 9.9 10.6 57.5 3.7 7.4 Compared with the untreated test polyamide PA 6I / MXDI (Comparative Example 1), the addition of 0.1% by weight of a UV absorber to the test polyamide reduces the transmission of light having a wavelength of 380, 385 and 400 nm at the test specimen in each case was measured. The two UV absorbers D (Example 5) and E (Example 6) gave the best results, without the light transmission deteriorated considerably. This was in any case higher than 91%. Likewise a rather good reduction of the transmission of light with a wavelength of 380, 385 and 400 nm was achieved with the UV absorbers A (Comparative Example 2) and B (Comparative Example 3). In addition, it was found that the yellow index worsened when irradiating the specimens with sunlight (Suntest). However, even with the untreated test nylon PA 6I / MXDI the yellow index, ie the yellowing, increased due to the irradiation with sunlight. The Haze value was alright in all cases.

Im folgenden werden an Hand der Tabelle 5 die erhaltenen Resultate an Hand des verwendeten Testpolyamids PA MACM12 gezeigt und anschliessend erläutert: Vergleichsbeispiele Beispiele Komponenten: Einheit 7 8 9 10 11 12 13 PA MACM12 Gew.-% 100.0 99.8 99.8 99.8 99.8 99.8 99.8 UV-Absorber A Gew.-% - 0.2 - 0.1 - - - UV-Absorber B Gew.-% - - 0.2 0.1 - 0.05 0.1 UV-Absorber D Gew.-% - - - - 0.2 0.15 0.1 Tests: Haze % 0.4 0.5 0.6 0.5 0.6 0.3 0.4 Lichttransmission % 92.3 91.7 91.7 91.7 92.0 92.0 92.0 YI ASTM D 1925 original -2.4 5.9 5.2 5.2 0.8 -0.7 -0.7 Suntest -1.4 3.9 3.0 3.0 6.1 3.4 0.7 Transmission 380 nm, % 82.7 0.1 0.0 0.0 0.1 0.0 0.1 Transmission 385 nm, % 83.8 0.2 0.7 0.3 0.3 0.2 0.3 Transmission 400 nm, % 86.2 3.1 50.3 22.4 4.0 8.4 16.8 Verglichen mit dem unbehandelten Testpolyamid PA MACM12 (Vergleichsbeispiel 7), reduziert die Zugabe von insgesamt 0.2 Gew.-% eines oder zweier UV-Absorber zum Testpolyamid in jedem Fall die Transmission von Licht mit einer Wellenlänge von 380, 385 und 400 nm, die am Prüfkörper gemessen wurde. Dabei ergab der UV-Absorber D (Beispiel 11) ein gutes Resultat, ohne dass sich die Lichttransmission erheblich verschlechterte. Diese war in jedem Fall höher als 91 %. Ebenfalls eine recht gute Reduktion der Transmission von Licht mit einer Wellenlänge von 380, 385 und 400 nm wurde mit dem UV-Absorber A (Vergleichsbeispiel 8) erreicht. Zudem zeigte sich, dass sich der Yellow-Index beim Bestrahlen der Prüfkörper mit Sonnenlicht (Suntest) verschlechterte. Allerdings stieg auch beim unbehandelten Testpolyamid PA MACM12 der Yellow-Index, also die Vergilbung, durch die Bestrahlung mit Sonnenlicht leicht an. Es fällt auf, dass sich bei einer Kombination der UV-Absorber B und D (Beispiele 12 und 13) gegenüber der Verwendung von einem UV-Absorber D (Beispiel 11) der Haze-Wert und das Suntest-Resultat verbesserte. Allerdings musste eine leicht höhere (schlechtere) Transmission von Licht mit einer Wellenlänge von 400 nm festgestellt werden. Der UV-Absorber B führt bei diesem Testpolyamid PA MACM12 zu einem wesentlich schlechteren Resultat als zum vorher geprüften Testpolyamid PA 6I/MXDI.In the following, with reference to Table 5, the results obtained are shown with reference to the test polyamide PA MACM12 used and then explained below: Comparative Examples Examples components: unit 7 8th 9 10 11 12 13 PA MACM12 Wt .-% 100.0 99.8 99.8 99.8 99.8 99.8 99.8 UV absorber A Wt .-% - 0.2 - 0.1 - - - UV absorber B Wt .-% - - 0.2 0.1 - 12:05 0.1 UV absorber D Wt .-% - - - - 0.2 12:15 0.1 Testing: Haze % 0.4 0.5 0.6 0.5 0.6 0.3 0.4 light transmission % 92.3 91.7 91.7 91.7 92.0 92.0 92.0 YI ASTM D 1925 original -2.4 5.9 5.2 5.2 0.8 -0.7 -0.7 suntest -1.4 3.9 3.0 3.0 6.1 3.4 0.7 transmission 380 nm,% 82.7 0.1 0.0 0.0 0.1 0.0 0.1 transmission 385 nm,% 83.8 0.2 0.7 0.3 0.3 0.2 0.3 transmission 400 nm,% 86.2 3.1 50.3 22.4 4.0 8.4 16.8 Compared with the untreated test polyamide PA MACM12 (Comparative Example 7), the addition of a total of 0.2% by weight of one or two UV absorbers to the test polyamide reduces in each case the transmission of light having a wavelength of 380, 385 and 400 nm Test specimen was measured. In this case, the UV absorber D (Example 11) gave a good result, without the light transmission deteriorated significantly. This was in any case higher than 91%. Likewise a rather good reduction of the transmission of light with a wavelength of 380, 385 and 400 nm was achieved with the UV absorber A (Comparative Example 8). In addition, it was found that the yellow index worsened when irradiating the specimens with sunlight (Suntest). However, even with the untreated test polyamide PA MACM12, the yellow index, ie the yellowing, increased slightly due to exposure to sunlight. It stands out that at a combination of the UV absorbers B and D (Examples 12 and 13) over the use of a UV absorber D (Example 11) the Haze value and the Suntest result improved. However, a slightly higher (worse) transmission of light with a wavelength of 400 nm had to be detected. The UV absorber B results in this test PA PA MACM12 to a much poorer result than the previously tested PA 6I / MXDI test nylon.

Im folgenden werden an Hand der Tabelle 6 die erhaltenen Resultate an Hand des verwendeten Testpolyamids PA MACMI/MACMT/12 gezeigt und anschliessend erläutert: Vergleichsbeispiele Beispiele Komponenten: Einheit 14 15 16 17 18 PA MACMI/MACMT/12 Gew.-% 100.0 99.8 99.8 99.8 99.8 UV-Absorber A Gew.-% - 0.2 - - - UV-Absorber D Gew.-% - - 0.2 - 0.1 UV-Absorber E Gew.-% - - - 0.2 0.1 Tests: Haze % 0.4 0.5 0.4 0.5 0.4 Lichttransmission % 93.5 93.1 92.9 93.0 93.0 YI ASTM D 1925 original 0.0 6.1 4.9 5.0 4.9 Suntest 2.0 4.3 3.0 3.2 3.1 Transmission 380 nm, % 66.9 0.0 0.0 0.0 0.0 Transmission 385 nm, % 69.3 0.3 0.2 0.2 0.2 Transmission 400 nm, % 76.2 6.4 2.6 4.7 3.0 Verglichen mit dem unbehandelten Testpolyamid PA MACMI/MACMT/12 (Vergleichsbeispiel 14), reduziert die Zugabe von 0.2 Gew.-% eines UV-Absorbers zum Testpolyamid in jedem Fall die Transmission von Licht mit einer Wellenlänge von 380, 385 und 400 nm, die am Prüfkörper gemessen wurde. Dabei ergaben die UV-Absorber D (Beispiel 16) und E (Beispiel 17) ein gutes Resultat, ohne dass sich die Lichttransmission erheblich verschlechterte. Ein ebenfalls gutes Resultat ergab sich aus der Zugabe einer Mischung der beiden UV-Absorber D und E (Beispiel 18) zur Polyamidformmassen-Schmelze. Die gemessene Lichttransmission war in jedem Fall höher als 92 %. Ebenfalls eine recht gute Reduktion der Transmission von Licht mit einer Wellenlänge von 380, 385 und 400 nm wurde mit dem UV-Absorber A (Vergleichsbeispiel 15) erreicht. Zudem zeigte sich, dass sich der Yellow-Index beim Bestrahlen der Prüfkörper mit Sonnenlicht (Suntest) nur beim unbehandelten Testpolyamid PA MACMI/MACMT/12 verschlechterte; das Hinzufügen eines UV-Absorber A (Vergleichsbeispiel 15), D (Beispiel 16), E (Beispiel 17) oder einer Mischung der UV-Absorber D und E (Beispiel 18) ergab nach der Bestrahlung mit Sonnenlicht sogar eine geringere Vergilbung. Der Haze-Wert war in allen Fällen in Ordnung.The results obtained are shown below with reference to Table 6 using the test polyamide PA MACMI / MACMT / 12 and then explained below: Comparative Examples Examples components: unit 14 15 16 17 18 PA MACMI / MACMT / 12 Wt .-% 100.0 99.8 99.8 99.8 99.8 UV absorber A Wt .-% - 0.2 - - - UV absorber D Wt .-% - - 0.2 - 0.1 UV absorber E Wt .-% - - - 0.2 0.1 Testing: Haze % 0.4 0.5 0.4 0.5 0.4 light transmission % 93.5 93.1 92.9 93.0 93.0 YI ASTM D 1925 original 0.0 6.1 4.9 5.0 4.9 suntest 2.0 4.3 3.0 3.2 3.1 transmission 380 nm,% 66.9 0.0 0.0 0.0 0.0 transmission 385 nm,% 69.3 0.3 0.2 0.2 0.2 transmission 400 nm,% 76.2 6.4 2.6 4.7 3.0 Compared to the untreated test polyamide PA MACMI / MACMT / 12 (Comparative Example 14), the addition of 0.2% by weight of a UV absorber to the test polyamide in each case reduces the transmission of light having a wavelength of 380, 385 and 400 nm, the was measured on the specimen. The UV absorbers D (Example 16) and E (Example 17) gave a good result without the light transmission deteriorating significantly. A likewise good result resulted from the addition of a mixture of the two UV absorbers D and E (Example 18) to the polyamide molding material melt. The measured light transmission was always higher than 92%. Likewise a rather good reduction of the transmission of light with a wavelength of 380, 385 and 400 nm was achieved with the UV absorber A (Comparative Example 15). In addition, it was found that the yellow index on irradiation of the test specimens with sunlight (Suntest) only deteriorated in the case of the untreated test polyamide PA MACMI / MACMT / 12; the addition of a UV absorber A (Comparative Example 15), D (Example 16), E (Example 17) or a mixture of UV absorbers D and E (Example 18) gave even less yellowing after exposure to sunlight. The Haze value was alright in all cases.

Im folgenden werden an Hand der Tabelle 7 die erhaltenen Resultate an Hand des verwendeten Testpolyamids PA 6I/6T/MACMI/MACMT/PACMI/PACMT/12 gezeigt und anschliessend erläutert: Vergleichsbeispiele Beispiele Komponenten: Einheit 19 20 21 22 23 PA 6I/6T/MACMI/ MACMT/ PACMI/PACMT/12 Gew.-% 100.0 99.8 99.8 99.8 99.8 UV-Absorber A Gew.-% - 0.2 - - - UV-Absorber D Gew.-% - - 0.2 - 0.1 UV-Absorber E Gew.-% - - - 0.2 0.1 Tests: Haze % 0.4 0.4 0.4 0.4 0.4 Lichttransmission % 92.5 92.0 92.0 92.1 92.0 YI ASTM D 1925 original 0.0 7.2 5.1 5.6 5.3 Suntest 5.0 9.7 7.8 8.9 8.4 Transmission 380 nm, % 67.8 0.0 0.0 0.0 0.0 Transmission 385 nm, % 70.9 0.3 0.2 0.2 0.2 Transmission 400 nm, % 77.7 6.3 2.8 4.8 3.4 Verglichen mit dem unbehandelten Testpolyamid PA 6I/6T/MACMI/MACMT/ PACMI/PACMT/12 (Vergleichsbeispiel 19), reduziert die Zugabe von 0.2 Gew.-% eines UV-Absorbers zum Testpolyamid in jedem Fall die Transmission von Licht mit einer Wellenlänge von 380, 385 und 400 nm, die am Prüfkörper gemessen wurde. Dabei ergaben die UV-Absorber D (Beispiel 21) und E (Beispiel 22) ein gutes Resultat, ohne dass sich die Lichttransmission erheblich verschlechterte. Diese war in jedem Fall höher als 92 %. Ebenfalls eine recht gute Reduktion der Transmission von Licht mit einer Wellenlänge von 380, 385 und 400 nm wurde mit einer Mischung der beiden UV-Absorber D und E (Beispiel 23) und auch mit dem UV-Absorber A (Vergleichsbeispiel 20) erreicht. Zudem zeigte sich, dass sich der Yellow-Index beim Bestrahlen der Prüfkörper mit Sonnenlicht (Suntest) verschlechterte. Allerdings stieg auch beim unbehandelten Testpolyamid 6I/6T/MACMI/MACMT/PACMI/PACMT/12 der Yellow-Index, also die Vergilbung, durch die Bestrahlung mit Sonnenlicht leicht an. Der Haze-Wert war in allen Fällen in Ordnung.The results obtained are shown below with reference to Table 7 using the test polyamide PA 6I / 6T / MACMI / MACMT / PACMI / PACMT / 12 and then explained below: Comparative Examples Examples components: unit 19 20 21 22 23 PA 6I / 6T / MACMI / MACMT / PACMI / PACMT / 12 Wt .-% 100.0 99.8 99.8 99.8 99.8 UV absorber A Wt .-% - 0.2 - - - UV absorber D Wt .-% - - 0.2 - 0.1 UV absorber E Wt .-% - - - 0.2 0.1 Testing: Haze % 0.4 0.4 0.4 0.4 0.4 light transmission % 92.5 92.0 92.0 92.1 92.0 YI ASTM D 1925 original 0.0 7.2 5.1 5.6 5.3 suntest 5.0 9.7 7.8 8.9 8.4 transmission 380 nm,% 67.8 0.0 0.0 0.0 0.0 transmission 385 nm,% 70.9 0.3 0.2 0.2 0.2 transmission 400 nm,% 77.7 6.3 2.8 4.8 3.4 Compared with the untreated test nylon PA 6I / 6T / MACMI / MACMT / PACMI / PACMT / 12 (Comparative Example 19), the addition of 0.2% by weight of a UV absorber to the test polyamide in each case reduces the transmission of light having a wavelength of 380, 385 and 400 nm, which was measured on the test specimen. The UV absorbers D (Example 21) and E (Example 22) gave a good result without the light transmission deteriorating significantly. This was in any case higher than 92%. Likewise, a rather good reduction in the transmission of light having a wavelength of 380, 385 and 400 nm was achieved with a mixture of the two UV absorbers D and E (Example 23) and also with the UV absorber A (Comparative Example 20). In addition, it was found that the yellow index worsened when irradiating the specimens with sunlight (Suntest). However, the untreated test nylon 6I / 6T / MACMI / MACMT / PACMI / PACMT / 12 also showed a yellow index, ie yellowing, lightly by irradiation with sunlight. The Haze value was alright in all cases.

Aus den bisher gezeigten Testes kann abgeleitet werden, dass eine Verwendung der UV-Absorber A, D oder E bei allen vier Testpolyamiden zu akzeptablen Messwerten führt. Nun soll das Verursachen von Ablagerungen an den Oberflächen der Kavität einer Spritzgussform Auskunft darüber geben, welche Polyamid-UV-Absorber-Kombinationen sich beispielsweise für die Serienherstellung von spritzgegossenen Polyamidlinsen eigenen. Als Mass wurde die Anzahl der Spritzgusszyklen genommen, bis sichtbare Ablagerungen auf diesen Oberflächen festgestellt werden konnten.It can be deduced from the tests shown so far that use of the UV absorbers A, D or E leads to acceptable measured values for all four test polyamides. Now, the cause of deposits on the surfaces of the cavity of an injection mold should provide information about which polyamide UV absorber combinations are suitable, for example, for the series production of injection-molded polyamide lenses. As a measure, the number of injection molding cycles was taken until visible deposits on these surfaces could be detected.

Aus ökonomischen Gründen wurden diese Tests nach 250 Spritzgusszyklen abgebrochen, falls bis dahin noch kein Belag sichtbar und somit die Qualität der Formteile einwandfrei war.For economic reasons, these tests were terminated after 250 injection molding cycles, if so far no coating was visible and thus the quality of the molded parts was flawless.

Im folgenden werden an Hand der Tabelle 8 die erhaltenen Resultate an Hand der verwendeten Testpolyamide PA MACM12 und PA MACMI/12 gezeigt und anschliessend erläutert: Vergleichsbeispiele Beispiele Komponenten: Einheit 24 25 26 27 28 29 30 PA MACM12 Gew.-% 99.6 99.6 99.6 - 99.6 99.6 99.6 PA MACMI/12 Gew.-% - - - 99.6 - - - UV-Absorber A Gew.-% 0.4 0.2 0.4 - - - UV-Absorber B Gew.-% - 0.2 0.4 - - - - UV-Absorber D Gew.-% - - - - 0.4 - 0.2 UV-Absorber E Gew.-% - - - - - 0.4 0.2 Tests: Anzahl Spritzguss-Zyklen bis Ablagerungen sichtbar sind 60 90 > 250 58 > 250 > 250 > 250 Haze % 0.9 0.7 0.6 0.6 0.7 0.7 0.7 Lichttransmission % 91.4 91.5 91.6 91.9 91.8 91.9 91.9 YI ASTM D 1925 original 12.0 7.1 6.0 11.3 1.7 1.9 1.7 Suntest - - - - - - - Transmission 380 nm, % 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Transmission 385 nm, % - - - - 0.0 0.0 0.0 Transmission 400 nm, % 0.6 3.2 28.0 0.6 0.3 0.9 0.6 The results obtained are shown below with reference to the test polyamides PA MACM12 and PA MACMI / 12 used and then explained below with reference to Table 8 : Comparative Examples Examples components: unit 24 25 26 27 28 29 30 PA MACM12 Wt .-% 99.6 99.6 99.6 - 99.6 99.6 99.6 PA MACMI / 12 Wt .-% - - - 99.6 - - - UV absorber A Wt .-% 0.4 0.2 0.4 - - - UV absorber B Wt .-% - 0.2 0.4 - - - - UV absorber D Wt .-% - - - - 0.4 - 0.2 UV absorber E Wt .-% - - - - - 0.4 0.2 Testing: Number of injection molding cycles until deposits are visible 60 90 > 250 58 > 250 > 250 > 250 Haze % 0.9 0.7 0.6 0.6 0.7 0.7 0.7 light transmission % 91.4 91.5 91.6 91.9 91.8 91.9 91.9 YI ASTM D 1925 original 12.0 7.1 6.0 11.3 1.7 1.9 1.7 suntest - - - - - - - transmission 380 nm,% 0.0 0.0 0.0 0.0 0.0 0.0 0.0 transmission 385 nm,% - - - - 0.0 0.0 0.0 transmission 400 nm,% 0.6 3.2 28.0 0.6 0.3 0.9 0.6

Die bisher aussichtsreichsten UV-Absorber zum Einarbeiten in eine Polyamidformmassen-Schmelze A, D und E, sowie die Mischung aus den UV-Absorbern D und E zeigten eine sehr unterschiedliche Neigung zur Bildung von Ablagerungen auf der Oberfläche des Werkzeugs:

  • Der bisherige Mitfavorit, UV-Absorber A verursachte zusammen mit den Testpolyamiden PA MACM12 (Vergleichsbeispiel 24) bzw. PA MACMI/12 (Vergleichsbeispiel 27) schon nach 60 bzw. 58 Spritzgusszyklen sichtbare Ablagerungen und fällt damit aus der Evaluation.
  • Der UV-Absorber B verursacht auch nach 250 Zyklen keine sichtbaren Ablagerungen; er kann den gestellten Anforderungen jedoch nicht genügen, weil er beim Testpolyamid PA MACM12 eine wesentlich höhere (schlechtere) Transmission von Licht mit einer Wellenlänge von 400 nm zulässt (vgl. Tabelle 5).
The previously most promising UV absorbers for incorporation into a polyamide molding compound melt A, D and E, and the mixture of the UV absorbers D and E showed a very different tendency to form deposits on the surface of the tool:
  • The previous co-favorite, UV absorber A, together with the test polyamides PA MACM12 (Comparative Example 24) and PA MACMI / 12 (Comparative Example 27) caused visible deposits even after 60 or 58 injection molding cycles and thus falls out of the evaluation.
  • The UV absorber B causes no visible deposits even after 250 cycles; However, it can not meet the requirements set because it allows a much higher (worse) transmission of light with a wavelength of 400 nm for the test polyamide PA MACM12 (see Table 5).

Der UV-Absorber C wurde nicht zum Zyklus-Test zugelassen, weil er beim Testpolyamid PA 6I/MXDI eine wesentlich höhere (schlechtere) Transmission von Licht bei allen gemessenen Wellenlängen 380, 385 und 400 nm zulässt (vgl. Tabelle 4).The UV absorber C was not approved for the cycle test, because it allows for the test nylon PA 6I / MXDI a significantly higher (worse) transmission of light at all measured wavelengths 380, 385 and 400 nm (see Table 4).

Der UV-Absorber D überzeugt bei den physikalischen Messwerten, wenn er in eine Polyamidformmassen-Schmelze eingearbeitet wurde. Dies gilt für alle verwendeten Testpolyamide PA 6I/MXDI (vgl. Tabelle 4: Beispiel 5), PA MACM12 (vgl. Tabelle 5: Beispiel 11), PA MACMI/MACMT/12 (vgl. Tabelle 6: Beispiel 16) und PA 6I/6T/MACMI/MACMT/PACMI/PACMT/12 (vgl. Tabelle 7: Beispiel 21). Dieser UV-Absorber D verursacht in Kombination mit dem Testpolyamid PA MACM12 (vgl. Tabelle 8: Beispiel 28) auch nach 250 Zyklen keine sichtbaren Ablagerungen. Der UV-Absorber D erfüllt somit alle an ihn gestellten Anforderungen und ist ein erfindungsgemässer UV-Absorber in einer Polyamidformmassen-Schmelze.The UV absorber D impresses with its physical measurements when it has been incorporated into a polyamide molding material melt. This applies to all test polyamides used PA 6I / MXDI (see Table 4: Example 5), PA MACM12 (see Table 5: Example 11), PA MACMI / MACMT / 12 (see Table 6: Example 16) and PA 6I / 6T / MACMI / MACMT / PACMI / PACMT / 12 (see Table 7: Example 21). This UV absorber D in combination with the test polyamide PA MACM12 (see Table 8: Example 28) causes no visible deposits even after 250 cycles. The UV absorber D thus fulfills all requirements imposed on it and is a UV absorber according to the invention in a polyamide molding material melt.

Der UV-Absorber E überzeugt bei den physikalischen Messwerten, wenn er in eine Polyamidformmassen-Schmelze eingearbeitet wurde. Dies gilt für alle Testpolyamide PA 6I/MXDI (vgl. Tabelle 4: Beispiel 6), PA MACMI/MACMT/12 (vgl. Tabelle 6: Beispiel 17) und PA 6I/6T/MACMI/MACMT/PACMI/PACMT/12 (vgl. Tabelle 7: Beispiel 22) in denen er geprüft wurde. Der UV-Absorber E verursacht in Kombination mit dem Testpolyamid PA MACM12 (vgl. Tabelle 8: Beispiel 29) auch nach 250 Zyklen keine sichtbaren Ablagerungen. Der UV-Absorber E erfüllt somit alle an ihn gestellten Anforderungen und ist ein erfindungsgemässer UV-Absorber in einer Polyamidformmassen-Schmelze.The UV absorber E impresses with the physical measured values when it has been incorporated into a polyamide molding material melt. This applies to all test polyamides PA 6I / MXDI (compare Table 4: Example 6), PA MACMI / MACMT / 12 (see Table 6: Example 17) and PA 6I / 6T / MACMI / MACMT / PACMI / PACMT / 12 (see Table 7: Example 22) in which it was tested. The UV absorber E in combination with the test polyamide PA MACM12 (see Table 8: Example 29) causes no visible deposits even after 250 cycles. The UV absorber E thus fulfills all the requirements placed on it and is a UV absorber according to the invention in a polyamide molding material melt.

Die Kombination der UV-Absorber D und E überzeugt bei den physikalischen Messwerten, wenn sie in eine Polyamidformmassen-Schmelze eingearbeitet wurde (vgl. Beispiele 23 und 30) und zeigt mit dem Testpolyamid PA MACM12 (vgl. Tabelle 8: Beispiel 30) auch nach 250 Zyklen keine sichtbaren Ablagerungen. Die Kombination der UV-Absorber D und E erfüllt somit alle an sie gestellten Anforderungen und ist eine erfindungsgemäss bevorzugte UV-Absorber-Kombination in einer Polyamidformmassen-Schmelze.The combination of the UV absorbers D and E is convincing in the case of the physical measured values when it has been incorporated into a polyamide molding compound melt (compare Examples 23 and 30) and also shows with the test polyamide PA MACM12 (see Table 8: Example 30) 250 cycles no visible deposits. The combination of the UV absorbers D and E thus fulfills all the requirements imposed on them and is a preferred UV absorber combination according to the invention in a polyamide molding material melt.

Das Kriterium der unterschiedlichen Neigung zur Bildung von Ablagerungen auf der Oberfläche des Werkzeugs ist stichhaltig, weil eine solche Belagsbildung die Qualität der Oberflächen der mit diesen UV-Absorbern hergestellten Spritzgussteile erheblich beeinträchtigt. Die gleichen Polyamidformmassen-Schmelzen ohne diese UV-Absorber verursachten keine solche unerwünschte Belagsbildung, so dass diese eindeutig den verwendeten UV-Absorbern zugeordnet werden muss.The criterion of the different tendency to form deposits on the surface of the tool is valid, because such a deposit formation significantly affects the quality of the surfaces of the injection molded parts produced with these UV absorbers. The same polyamide molding material melts without these UV absorbers caused no such unwanted deposit formation, so that they must be clearly assigned to the UV absorbers used.

Wie die in Tabelle 8 angegebenen Transmissionswerte zeigen, ist es durch die Verwendung von 0.4 Gew.-% UV-Absorber A, D, E bzw. der Kombination D und E durchaus möglich die Transmission auf unter 1 % zu senken. Bei Verwendung des UV-Absorbers A in dieser Menge steigt aber der Yellow-Index drastisch an, so dass ein Wert von 12 resultiert (vgl. Vergleichsbeispiel 24).As shown in Table 8 transmission values, it is by the use of 0.4 wt .-% UV absorber A, D, E or the combination D and E quite possible to reduce the transmission to less than 1%. When using the UV absorber A in this amount, however, the yellow index increases drastically, so that a value of 12 results (compare Comparative Example 24).

Bei Verwendung der erfindungsgemässen UV-Absorber D, E oder deren Mischung ist die Zunahme des Yellow-Indexes bei weitem geringer, so dass Werte unter 2 resultieren (vgl. Beispiele 28, 29 und 30).When using the novel UV absorbers D, E or their mixture, the increase in the yellow index is far lower, so that values below 2 result (compare Examples 28, 29 and 30).

Eine zweite Testserie, bei welcher Masterbatches verwendet wurden, bestätigte die eben diskutierten Ergebnisse des Zyklus-Tests. Im folgenden werden an Hand der Tabelle 9 die erhaltenen Resultate an Hand des verwendeten Testpolyamids PA MACM12 gezeigt und anschliessend erläutert: Vergleichsbeispiel Beispiele Komponenten: Einheit 31 32 33 PA MACM12 Gew.-% 95 95 95 UV-Masterbatch F Gew.-% 5 - - UV-Masterbatch G Gew.-% - 5 - UV-Masterbatch H Gew.-% - - 5 Tests: Anzahl Spritzguss-Zyklen bis Ablagerungen sichtbar sind 58 >250 > 250 A second series of tests using masterbatches confirmed the results of the cycle test just discussed. The results obtained are shown below with reference to Table 9 using the test polyamide PA MACM12 used and then explained below: Comparative example Examples components: unit 31 32 33 PA MACM12 Wt .-% 95 95 95 UV Masterbatch F Wt .-% 5 - - UV masterbatch G Wt .-% - 5 - UV Masterbatch H Wt .-% - - 5 Testing: Number of injection molding cycles until deposits are visible 58 > 250 > 250

Von dem UV-Masterbatch F (Vergleichsbeispiel 31) mit 8 % des UV-Absorbers A (vgl. Tabelle 3) wurden 5 Gew.-% zu dem Testpolyamid PA MACM12 zugegeben. Somit beträgt der Anteil des UV-Absorbers A in Bezug auf das Testpolyamid 0.4 Gew.-%. Ähnlich, wie schon in Tabelle 8 gezeigt (siehe Vergleichsbeispiel 24) verursacht der UV-Absorber A zusammen mit dem Testpolyamid PA MACM12 diesmal bereits nach 58 Spritzgusszyklen sichtbare Ablagerungen.Of the UV masterbatch F (Comparative Example 31) with 8% of the UV absorber A (see Table 3), 5% by weight was added to the test nylon PA MACM12. Thus, the proportion of the UV absorber A with respect to the test polyamide is 0.4 wt .-%. Similarly, as already shown in Table 8 (see Comparative Example 24), the UV absorber A together with the test polyamide PA MACM12 causes visible deposits already after 58 injection cycles.

Von dem UV-Masterbatch G (Beispiel 32) mit 8 % des UV-Absorbers D (vgl. Tabelle 3) wurden 5 Gew.-% zu dem Testpolyamid PA MACM12 zugegeben. Somit beträgt der Anteil des UV-Absorbers D in Bezug auf das Testpolyamid 0.4 Gew.-%. Gerade so wie schon in Tabelle 8 gezeigt (vgl. Beispiel 28) verursacht der UV-Absorber D in Kombination mit dem Testpolyamid PA MACM12 (vgl. Tabelle 9; Beispiel 32) auch nach 250 Zyklen keine sichtbaren Ablagerungen.Of the UV masterbatch G (Example 32) with 8% of the UV absorber D (see Table 3), 5% by weight was added to the test nylon PA MACM12. Thus, the proportion of UV absorber D with respect to the test polyamide is 0.4% by weight. Just as shown in Table 8 (see Example 28), the UV absorber D in combination with the test polyamide PA MACM12 (see Table 9, Example 32) causes no visible deposits even after 250 cycles.

Von dem UV-Masterbatch H (Beispiel 33) mit 7 % des UV-Absorbers D und 1 % des UV-Absorbers B (vgl. Tabelle 3) wurden 5 Gew.-% zu dem Testpolyamid PA MACM12 zugegeben. Somit beträgt der Anteil des UV-Absorber-Gemisches D/B in Bezug auf das Testpolyamid 0.4 Gew.-%. Die Anwesenheit beider UV-Absorber B und D verursacht somit in Kombination mit dem Testpolyamid PA MACM12 auch nach 250 Zyklen keine sichtbaren Ablagerungen. Dieses Ergebnis ist auch deshalb von Interesse, weil eine ähnliche Kombination von 0.05 Gew.-% des UV-Absorbers B und 0.15 Gew.-% des UV-Absorbers D (vgl. Tabelle 5, Beispiel 12) einen verbesserten Haze-Wert und Yellow-Index ergab; dabei musste nur ein leicht schlechterer Transmissionswert von Licht mit einer Wellenlänge von 400 nm gegenüber der Verwendung von nur UV-Absorber D in Kauf genommen werden.Of the UV masterbatch H (Example 33) with 7% of the UV absorber D and 1% of the UV absorber B (see Table 3), 5% by weight was added to the test nylon PA MACM12. Thus, the proportion of the UV absorber mixture D / B with respect to the test polyamide is 0.4 wt .-%. The presence of both UV absorbers B and D thus causes no visible deposits even after 250 cycles in combination with the test polyamide PA MACM12. This result is also of interest because a similar combination of 0.05% by weight of the UV absorber B and 0.15% by weight of the UV absorber D (see Table 5, Example 12) improved haze and yellow index; only a slightly worse transmission value of light with a wavelength of 400 nm compared to the use of only UV absorber D had to be accepted.

Auf Grund der vorliegenden Testergebnisse werden erfindungsgemäss die beiden UV-Absorber D oder E zu einer Polyamidformmassen-Schmelze gegeben, mit welcher transparente, für Licht bis zu einer Wellenlänge von 400 nm eine reduzierte Transmission aufweisende Kunststoff-Produkte hergestellt werden sollen. Der Anteil eines dieser zugegebenen UV-Absorber beträgt vorzugsweise zwischen 0.01 und 1.0 Gew.-%, besonders bevorzugt zwischen 0.05 und 0.4 Gew.-%, bezogen auf das Gewicht der Polyamidformmasse.On the basis of the present test results, according to the invention, the two UV absorbers D or E are added to a polyamide molding compound melt, with which transparent plastic products having a reduced transmission for light up to a wavelength of 400 nm are to be produced. The proportion of one of these added UV absorbers is preferably between 0.01 and 1.0 wt .-%, more preferably between 0.05 and 0.4 wt .-%, based on the weight of the polyamide molding composition.

Beide UV-Absorber ermöglichen, dass die diesen UV-Absorber umfassende Polyamidformmassen-Schmelze auf Oberflächen, mit denen sie in Kontakt kommt, keine sichtbare Belagsbildung verursacht:

  • Der UV-Absorber D, 1-(4-Metoxyphenyl)-3-(4-tert-butylphenyl)propan-1,3-dion, ist ein Vertreter der Dibenzoylmethane.
Both UV absorbers allow the polyamide molding material melt comprising this UV absorber to cause no visible deposit formation on surfaces with which it comes into contact:
  • The UV absorber D, 1- (4-methoxyphenyl) -3- (4-tert-butylphenyl) propane-1,3-dione, is a representative of dibenzoylmethane.

Der UV-Absorber E, 2-(4'-Diethylamino-2'-hydroxybenzoyl)benzoesäure-n-hexylester, ist ein Vertreter der Aminohydroxybenzoylbenzoesäureester.The UV absorber E, 2- (4'-diethylamino-2'-hydroxybenzoyl) benzoic acid n-hexyl ester, is a representative of Aminohydroxybenzoylbenzoesäureester.

Die beiden erfindungsgemässen UV-Absorber D und E weisen als gemeinsames chemisches Merkmal mindestens eine substituierte Benzoylgruppe auf.The two inventive UV absorbers D and E have as a common chemical feature at least one substituted benzoyl group.

Es ist bekannt, dass Avobenzone (auch bekannt unter der Bezeichnung Dibenzoylmethane oder Handelsnamen wie z.B. Parsol 1789; UV-Absorber D) unter der Belastung durch Sonnenlicht degradieren kann (siehe z.B. Warwick L. Morison, M.D. "Photosensitivity" The New England Journal of Medicine. Boston: Mar 11, 2004. Vol. 350, Iss. 11; pg. 1111 - 1117 ). Offenbar kann diese Degradation durch Zumischen des UV-Absorbers B vermindert werden (vgl. Tabelle 5, Beispiele 12 und 13).It is known that Avobenzone (also known as dibenzoylmethane or trade names such as Parsol 1789; UV absorber D) can degrade under exposure to sunlight (see, eg, US Pat Warwick L. Morison, MD "Photosensitivity" The New England Journal of Medicine. Boston: Mar 11, 2004. Vol. 350, Iss. 11; pg. 1111-1117 ). Apparently this degradation can be reduced by admixing the UV absorber B (see Table 5, Examples 12 and 13).

Ein weiterer Hinweis auf eine mögliche Stabilisation des UV-Absorbers D ergibt sich aus dem nächsten Beispiel. Im folgenden werden an Hand der Tabelle 10 die erhaltenen Resultate an Hand des verwendeten Testpolyamids PA MACM12 gezeigt und anschliessend erläutert: Beispiele Komponenten: Einheit 34 35 PA MACM12 Gew.-% 99.85 99.85 UV-Absorber D Gew.-% 0.15 0.15 Makrolex blau RR ppm - 1.4 Tests: Haze % 0.5 0.3 Lichttransmission % 92.0 90.8 YI ASTM D 1925 original 0.8 -3.7 Suntest 6.1 4.4 Transmission 380 nm, % 0.1 0.0 Transmission 385 nm, % 0.3 0.24 Transmission 400 nm, % 4.9 4.4 Another indication of a possible stabilization of the UV absorber D is shown in the next example. The results obtained are shown below with reference to Table 10 using the test polyamide PA MACM12 used and then explained below: Examples components: unit 34 35 PA MACM12 Wt .-% 99.85 99.85 UV absorber D Wt .-% 12:15 12:15 Makrolex blue RR ppm - 1.4 Testing: Haze % 0.5 0.3 light transmission % 92.0 90.8 YI ASTM D 1925 original 0.8 -3.7 suntest 6.1 4.4 transmission 380 nm,% 0.1 0.0 transmission 385 nm,% 0.3 12:24 transmission 400 nm,% 4.9 4.4

Eine Reduktion des UV-Absorber-Anteils von 0.2 Gew.-% (siehe Tabelle 5: Beispiel 11) auf 0.15 Gew.-% (Beispiel 34) zum Testpolyamid PA MACM12 ergibt einen leicht tieferen Haze-Wert und einen etwas erhöhten Transmissionswert bei 400 nm. Alle anderen Messwerte sind identisch. Gibt man aber nur 1.4 ppm des Farbstoffes Macrolex blau RR (LANXESS Deutschland GmbH, Leverkusen) dazu, so wird der Haze-Wert nochmals reduziert. Allerdings reduziert sich die Lichttransmission auch etwas, bleibt aber noch über 90 %. Deutlich reduziert sind insbesondere der Yellow-Index und der Transmissionswert für Licht mit einer Wellenlänge von 400 nm.A reduction of the UV absorber content from 0.2% by weight (see Table 5: Example 11) to 0.15% by weight (Example 34) for the test PA PA MACM12 gives a slightly lower Haze value and a somewhat increased transmission value at 400 nm. All other measurements are identical. If, however, only 1.4 ppm of the dye Macrolex blue RR (LANXESS Deutschland GmbH, Leverkusen) is added, the haze value is reduced again. However, the light transmission also reduces slightly, but still remains over 90%. In particular, the yellow index and the transmission value for light with a wavelength of 400 nm are significantly reduced.

Überraschenderweise stellte sich somit heraus, dass Polyamidformmassen-Schmelzen mit einem UV-Absorber in der Form einer Dibenzoylmethan-Verbindung D oder eines Aminohydroxybenzoylbenzoesäureesters E auf Oberflächen, mit denen diese Polyamidformmassen-Schmelzen in Kontakt kamen, keine sichtbare Belagsbildung verursachen.Surprisingly, it thus turned out that polyamide molding compound melts with a UV absorber in the form of a dibenzoylmethane compound D or an aminohydroxybenzoylbenzoic acid ester E on surfaces with which these polyamide molding compound melts came into contact do not cause visible deposit formation.

Überraschend wurden somit UV-Absorber gefunden, welche die gewünschten Eigenschaften in transparenten Polyamiden ermöglichen und welche sowohl die hohen Temperaturen bei der Verarbeitung oder Compoundierung der Formmasse als auch die sauren und alkalischen Endgruppen der Polyamide überstehen. Entgegen den Erwartungen, hervorgerufen durch den niedrigen Schmelzpunkt, neigen UV-Absorber des Typs Dibenzoylmethan bei der Einarbeitung in Polyamide oder bei der Verarbeitung dibenzoylmethanhaltiger Polyamidformmassen nicht zur Bildung sichtbarer Ablagerungen auf Plastifizierschnecken, Düsenlippen, Werkzeugoberflächen oder Kühlwalzen. Dieser Vorteil bleibt auch bei Kombination der Dibenzoylmethane mit unchlorierten Hydroxyphenylbenztriazolen erhalten.Surprisingly, therefore, UV absorbers have been found which enable the desired properties in transparent polyamides and which survive both the high temperatures during processing or compounding of the molding compound and the acidic and alkaline end groups of the polyamides. Contrary to expectations caused by the low melting point, UV absorbers of the dibenzoylmethane type do not tend to form visible deposits on plasticizing screws, die lips, tool surfaces or cooling rolls when incorporated into polyamides or when processing dibenzoylmethane-containing polyamide molding compositions. This advantage is retained even when combining the dibenzoylmethanes with unchlorinated hydroxyphenylbenzotriazoles.

Mit einer Beimischung von unchlorierten Hydroxyphenylbenztriazolen zu Dibenzoylmethanen kann überraschenderweise auch die Zunahme des Yellow-Index nach Belichtung verringert werden, wie die Beispiele 12 und 13 zeigen.With an admixture of unchlorinated hydroxyphenylbenzotriazoles to dibenzoylmethanes, surprisingly, the increase in the yellow index after exposure can also be reduced, as examples 12 and 13 show.

Aus diesen Gründen wird des weiteren eine Ausführungsform der erfindungsgemässen Polyamidformmassen-Schmelze bevorzugt, die dadurch gekennzeichnet ist, dass sie einen weiteren UV-Absorber umfasst, welcher dem zumindest einen UV-Absorber D oder E zugemischt ist. Dabei ist der weitere UV-Absorber ausgewählt aus einer Gruppe, die gebildet ist aus unchlorierten Hydroxyphenylbenztriazolen, Aminohydroxybenzoylbenzoesäureester und Dibenzoylmethanen. Speziell bevorzugt ist ein unchloriertes Hydroxyphenylbenztriazol in der Form von 2-(2H-Benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol. Ebenfalls speziell bevorzugt ist ein Aminohydroxybenzoylbenzoesäureester in der Form von 2-(4'-Diethylamino-2'-hydroxybenzoyl) benzoesäure-n-hexylester.For these reasons, an embodiment of the novel polyamide molding material melt is furthermore preferred, which is characterized in that it comprises a further UV absorber, which is admixed with the at least one UV absorber D or E. In this case, the further UV absorber is selected from a group which is formed from unchlorinated hydroxyphenylbenzotriazoles, aminohydroxybenzoylbenzoic acid esters and dibenzoylmethanes. Especially preferred is an unchlorinated hydroxyphenylbenzotriazole in the form of 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol. Also especially preferred is an aminohydroxybenzoylbenzoic acid ester in the form of 2- (4'-diethylamino-2'-hydroxybenzoyl) benzoic acid n-hexyl ester.

Eine andere Methode, diese Zunahme des Yellow-Index zu reduzieren, ist die Kombination der Dibenzoylmethane, bzw. das Mischen einer Verbindung, die mindestens eine substituierte Benzoylgruppe aufweist, mit Farbstoffen der Klasse der Anthrachinon-Farbstoffe, wie beispielsweise Macrolex blau RR oder Macrolex rot 5B, wie Beispiel 35 zeigt. Die Anthrachinon-Farbstoffe werden dabei in Mengen von 0.1 bis 1000 ppm, bevorzugt 0.5 bis 500 ppm eingesetzt. Eine Reduktion des Yellow-Index erzielen auch optische Aufheller wie Tinopal AMS GX oder Tinopal DMS.Another way to reduce this increase in yellow index is the combination of dibenzoylmethanes, or mixing a compound having at least one substituted benzoyl group, with dyes of the class of anthraquinone dyes, such as Macrolex blue RR or Macrolex red 5B, as example 35 shows. The anthraquinone dyes are used in amounts of 0.1 to 1000 ppm, preferably 0.5 to 500 ppm. A reduction The yellow index also achieve optical brighteners such as Tinopal AMS GX or Tinopal DMS.

Bevorzugt sind transparente Polyamide, die gebildet sind aus :

  • mindestens einem Diamin, ausgewählt aus einer Gruppe, die aus Ethylendiamin, Butandiamin, Hexamethylendiamin, Trimethylhexamethylendiamin, Methylpentandiamin, Bis(aminocyclohexyl)methan und seinen Alkylderivaten, Bis(aminocyclohexyl)propan und seinen Alkylderivaten, Isophorondiamin, Norbornandiamin, Bis(aminomethyl)norbornan, Xylylendiamin, Bis(aminomethyl)cyclohexan und seinen Alkylderivaten besteht, und
  • mindestens einer Dicarbonsäure, ausgewählt aus der Gruppe, die aus Bernsteinsäüre, Glutarsäure, Adipinsäure, Pimelinsäure, Korksäure, Azelainsäure, Sebazinsäure, Undecandisäure, Dodecandisäure, Brassylsäure, Tetradecandisäure, Pentadecandisäure, Hexadecandisäure, Heptadecandisäure, Octadecandisäure, Nonadecandisäure, Eicosandisäure, Japansäure, Cyclohexandicarbonsäure, Dimerfettsäure mit 36 oder 44 C-Atomen, Isophthalsäure, Terephthalsäure, Naphthalindicarbonsäure besteht.
Preference is given to transparent polyamides which are formed from:
  • at least one diamine selected from a group consisting of ethylenediamine, butanediamine, hexamethylenediamine, trimethylhexamethylenediamine, methylpentanediamine, bis (aminocyclohexyl) methane and its alkyl derivatives, bis (aminocyclohexyl) propane and its alkyl derivatives, isophoronediamine, norbornanediamine, bis (aminomethyl) norbornane, xylylenediamine , Bis (aminomethyl) cyclohexane and its alkyl derivatives, and
  • at least one dicarboxylic acid selected from the group consisting of succinic, glutaric, adipic, pimelic, succinic, azelaic, sebacic, undecanedioic, dodecanedioic, brassylic, tetradecanedioic, pentadecanedioic, hexadecanedioic, heptadecanedioic, octadecanedioic, nonadecanedioic, eicosanedioic, japanic, cyclohexanedicarboxylic, dimer fatty acids with 36 or 44 C atoms, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid.

Bevorzugt sind alternativ auch transparente Polyamide, die gebildet sind aus den vorgenannten Diaminen und Dicarbonsäuren sowie Lactamen mit 4 bis 15 C-Atomen und/oder α,ω-Aminosäuren mit 4 bis 15 C-Atomen.Also preferred are transparent polyamides, which are formed from the aforementioned diamines and dicarboxylic acids and lactams having 4 to 15 carbon atoms and / or α, ω-amino acids having 4 to 15 carbon atoms.

Speziell bevorzugte Diamine sind Hexamethylendiamin, Trimethylhexamethylendiamin, 2-Methyl-1,5-pentandiamin, Bis(4-amino-3-methyl-cyclohexyl)methan (abgekürzt MACM), Bis(4-amino-cyclohexyl)methan (abgekürzt PACM), Isophorondiamin, Norbornandiamin, m-Xylylendiamin und 1,3-Bis(aminomethyl)cyclohexan.Especially preferred diamines are hexamethylenediamine, trimethylhexamethylenediamine, 2-methyl-1,5-pentanediamine, bis (4-amino-3-methyl-cyclohexyl) methane (MACM for short), bis (4-amino-cyclohexyl) methane (abbreviated PACM), Isophoronediamine, norbornanediamine, m-xylylenediamine and 1,3-bis (aminomethyl) cyclohexane.

Speziell bevorzugte Dicarbonsäuren sind Adipinsäure, Azelainsäure, Sebazinsäure, 1,12-Dodecandisäure, Brassylsäure, 1,14-Tetradecandisäure, 1,15-Pentadecansäure, 1,16-Hexadecandisäure, 1,18-Octadecandisäure, 1,3-Cyclohexandicarbonsäure, 1,4-Cyclohexandicarbonsäure, Dimerfettsäure mit 36 oder 44 C-Atomen, Isophthalsäure, Terephthalsäure und 2,6-Naphthalindicarbonsäure.Especially preferred dicarboxylic acids are adipic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, brassylic acid, 1,14-tetradecanedioic acid, 1,15-pentadecanoic acid, 1,16-hexadecanedioic acid, 1,18-octadecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, dimer fatty acid having 36 or 44 carbon atoms, isophthalic acid, terephthalic acid and 2,6-naphthalenedicarboxylic acid.

Speziell bevorzugte Lactame sind Lactame bzw. α, ω-Aminosäuren mit 4, 6, 7, 8, 11 oder 12 C-Atomen. Dies sind die Lactame Pyrrolidin-2-on (4 C-Atome), ε-Caprolactam (6 C-Atome), Önanthlactam (7 C-Atome), Capryllactam (8 C-Atome), Laurinlactam (12 C-Atome) bzw. die α, ω-Aminosäuren 1,4-Aminobutansäure, 1,6-Aminohexansäure, 1,7-Aminoheptansäure, 1,8-Aminooctansäure, 1,11-Aminoundecansäure und 1,12-Aminododecansäure.Especially preferred lactams are lactams or α, ω-amino acids having 4, 6, 7, 8, 11 or 12 C atoms. These are the lactams pyrrolidin-2-one (4 C-atoms), ε-caprolactam (6 C-atoms), enanthlactam (7 C-atoms), capryllactam (8 C-atoms), laurolactam (12 C-atoms) resp the α, ω-amino acids 1,4-aminobutanoic acid, 1,6-aminohexanoic acid, 1,7-aminoheptanoic acid, 1,8-aminooctanoic acid, 1,11-aminoundecanoic acid and 1,12-aminododecanoic acid.

Ganz speziell bevorzugte transparente Polyamide mit hohen Brechungsindices sind PA 6I, PA 6I/6T, PA 6I/6T/6NDC, PA MXDI/6I, PA MXDI/MXDT/6I/6T, PA MXDI/12I, PA MXDI, mit mittleren und niederen Brechungsindices sind PA MACM12, PA MACM13, PA MACM14, PA MACM15, PA MACM16, PA MACM17, PA MACM18, PA 6-3-T, PA MACMI/12, PA MACM6/12, PA MACMT/12, PA MACMI/MACMNDC, PA MACMT/MACMNDC, PA MACMI/MACM36, PA MACMT/MACM36, PA MACMI/MACMT/12, PA 6I/MACMI/12, PA 6I/6T/MACMI/MACMT, PA 6I/6T/MACMI/MACMT/12, PA 6I/6T/MACMI/MACMT/MACM12/612, PA 6I/6T/6NDC/MACMI/MACMT/MACMNDC, wobei das MACM ganz oder teilweise durch PACM und/oder das ω-Laurolactam ganz oder teilweise durch ε-Caprolactam und/oder α, ω-Aminoundecansäure ersetzt sein kann.Especially preferred transparent polyamides with high refractive indices are PA 6I, PA 6I / 6T, PA 6I / 6T / 6NDC, PA MXDI / 6I, PA MXDI / MXDT / 6I / 6T, PA MXDI / 12I, PA MXDI, with middle and lower ones Refractive indices are PA MACM12, PA MACM13, PA MACM14, PA MACM15, PA MACM16, PA MACM17, PA MACM18, PA 6-3-T, PA MACMI / 12, PA MACM6 / 12, PA MACMT / 12, PA MACMI / MACMNDC, PA MACMT / MACMNDC, PA MACMI / MACM36, PA MACMT / MACM36, PA MACMI / MACMT / 12, PA 6I / MACMI / 12, PA 6I / 6T / MACMI / MACMT, PA 6I / 6T / MACMI / MACMT / 12, PA 6I / 6T / MACMI / MACMT / MACM12 / 612, PA 6I / 6T / 6NDC / MACMI / MACMT / MACMNDC, wherein all or part of the MACM is represented by PACM and / or the ω-laurolactam in whole or in part by ε-caprolactam and / or α, ω-aminoundecanoic acid may be replaced.

Transparente Polyamide können einen oder mehrere Zusatzstoffe ausgewählt aus der Gruppe aus Kondensationskatalysatoren, Kettenreglern, Entschäumern, Stabilisatoren, Gleitmitteln, Farbstoffen, Flammschutzmitteln, photochromen Additiven, Antistatika, Entformungsmitteln, optischen Aufhellern, natürlichen Schichtsilikaten, synthetischen Schichtsilikaten enthalten.Transparent polyamides may contain one or more additives selected from the group of condensation catalysts, chain regulators, defoamers, stabilizers, lubricants, dyes, flame retardants, photochromic additives, antistatic agents, mold release agents, optical brighteners, natural phyllosilicates, synthetic phyllosilicates.

Claims (17)

  1. A method for producing transparent polyamide moulded parts with a light transmission of at least 75% as measured according to ASTM 1003 at 2 mm thickness of the moulded part and a transmission of less than 20% of light with a wavelength of 400 nm at 2 mm thickness of the moulded part, characterized in that at least one UV absorber is incorporated into a molten polyamide moulding composition that can be processed thermoplastically, which UV absorber is selected from a group consisting of 1-(4-methoxyphenyl)-3-(4-tert-butylphenyl)-propane-1,3-dione and 2-(4'-diethylamino-2'-hydroxybenzoyl) benzoic acid n-hexyl ester, as a result of which said molten polyamide moulding composition, which comprises at least one of the UV absorbers, does not cause any visible deposit formation on surfaces with which it comes into contact during the production or processing of transparent polyamide moulded parts.
  2. Method according to claim 1, characterized in that the at least one UV absorber is a mixture of 1-(4-methoxyphenyl)-3-(4-tert-butylphenyl)-propane-1,3-dione and 2-(4'-diethylamino-2'-hydroxybenzoyl) benzoic acid n-hexyl ester.
  3. Method according to one of the preceding claims, characterized in that at least one further UV absorber is admixed to the at least one UV absorber, said further UV absorber being selected from a group which is formed from non-chlorinated hydroxyphenylbenztriazoles, aminohydroxybenzoyl benzoic acid esters and dibenzoylmethanes.
  4. Method according to one of the preceding claims, characterized in that a surface formed as the inner wall of a mould is free from visible deposit formation even after more than 250 processing cycles with the molten polyamide moulding composition comprising the at least one UV absorber.
  5. Method according to one of the claims 1 to 3, characterized in that the surface with which the molten polyamide moulding composition comes into contact is the surface of a plasticising screw, a mould and a cooling roll.
  6. Method according to one of the preceding claims, characterized in that the transparent polyamide moulded parts are selected from a group which comprises solar lenses, corrective lenses, non-corrective lenses, lenses for spectacles, parts of spectacles, protective goggles, windowpanes and protective panes, visors, displays, watch glasses, device housings, lamp covers, lenses for optical devices and systems, filters and films.
  7. A molten polyamide moulding composition that can be processed thermoplastically, comprising at least one UV absorber selected from a group consisting of 1-(4-methoxyphenyl)-3-(4-tert-butylphenyl)-propane-1,3-dione and 2-(4'-diethylamino-2'-hydroxybenzoyl) benzoic acid n-hexyl ester, characterized in that the molten polyamide moulding composition is formed from a transparent polyamide, a mixture of transparent polyamides, or a blend of transparent polyamides with at least one semicrystalline polyamide, wherein the transparent polyamide is formed from:
    (a) at least one diamine, selected from a group which consists of ethylenediamine, butanediamine, hexamethylenediamine, trimethylhexamethylenediamine, methylpentanediamine, bis(aminocyclohexyl) methane and its alkyl derivatives, bis(aminocyclohexyl) propane and its alkyl derivatives, isophoronediamine, norbornanediamine, bis(aminomethyl) norbornane, xylylenediamine, bis(aminomethyl) cyclohexane and its alkyl derivatives, and
    (b) at least one dicarboxylic acid selected from the group which consists of butanedioic acid, glutaric acid, adipinic acid, pimellic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, japanic acid, cyclohexanedicarboxylic acid, dimer fatty acid with 36 or 44 C-atoms, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, and optionally of
    (c) lactams with 4 to 15 C-atoms and/or α,ω-amino acids with 4 to 15 C-atoms.
  8. Molten polyamide moulding composition according to claim 7, characterized in that the at least one semicrystalline polyamide is selected from a group which is formed from PA 6, PA 46, PA 49, PA 410, PA 411, PA 412, PA 413, PA 414, PA 415, PA 416, PA 418, PA 436, PA 66, PA 69, PA 610, PA 611, PA 612, PA 613, PA 614, PA 615, PA 616, PA 617, PA 618, PA 66/6, PA 6/66/12, PA 6/12, PA 11, PA 12, PA 912, PA 1212, 6T/6I, MXD6, MXD6/MXDI, MXD9, MXD10, MXD11, MXD12, MXD13, MXD14, MXD15, MXD16, MXD17, MXD18, MXD36, PACM9, PACM10, PACM11, PACM12, PACM13, PACM14, PACM15, PACM16, PACM17, PACM18, PACM36, polyetheramides, polyetheresteramides and polyesteramides or their mixtures or copolymers.
  9. Molten polyamide moulding composition according to one of the claims 7 or 8, characterized in that the diamine is selected from a group which comprises hexamethylenediamine, trimethylhexamethylenediamine, 2-methyl-1,5-pentanediamine, bis(4-amino-3-methyl-cyclohexyl) methane, bis(4-aminocyclohexyl) methane, isophoronediamine, norbornanediamine, m-xylylenediamine and 1,3-bis(aminomethyl) cyclohexane.
  10. Molten polyamide moulding composition according to one of the claims 7 to 9, characterized in that the dicarboxylic acid is selected from a group which comprises adipinic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, brassylic acid, 1,14-tetradecanedioic acid, 1,15-pentadecanoic acid, 1,16-hexadecanoic acid, 1,18-octadecanoic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, dimer fatty acid with 36 or 44 C-atoms, isophthalic acid, terephthalic acid, and 2,6-naphthalenedicarboxylic acid.
  11. Molten polyamide moulding composition according to one of the claims 7 to 10, characterized in that the lactams respectively α,ω-amino acids comprise 4, 6, 7, 8, 11 or 12 C-atoms.
  12. Molten polyamide moulding composition according to one of the claims 7 to 11, characterized in that the transparent polyamides are selected from the group PA 61/6T/6NDC/MACMI/MACMT/MACMNDC, PA 61/6T/6NDC, PA MXDI/61, PA MXDI/MXDT/61/6T, PA 6I, PA 61/6T, PA MXDI/121, PA MXDI, PA MACM9, PA MACM10, PA MACM11, PA MACM12, PA MACM13, PA MACM 14, PA MACM 15, PA MACM16, PA MACM 17, PA MACM18, PA 6-3-T, PA MACMI/12, PA MACM6/12, PA MACMT/12, PA MACMI/MACMNDC, PA MACMT/MACMNDC, PA MACMI/MACM36, PA MACMT/MACM36, PA MACMI/MACMT/12, PA 61/MACMI/12, PA 61/6T/MACMI/MACMT, PA 61/6T/MACMI/MACMT/12, and PA 61/6T/MACMI/MACMT/MACM12/612, wherein optionally the MACM is replaced partly or entirely by PACM and/or the ω-laurolactam is replaced partly or entirely by ε-caprolactam and/or α,ω-aminoundecanoic acid.
  13. Molten polyamide moulding composition according to one of the claims 7 to 12, characterized in that a dye of the class of anthraquinone dyes is added to the polyamide moulding composition together with the at least one UV absorber selected from the group consisting of 1-(4-methoxyphenyl)-3-(4-tert-butylphenyl)-propane-1,3-dione and 2-(4'-diethylamino-2'-hydroxybenzoyl) benzoic acid n-hexyl ester.
  14. Transparent plastic moulded parts produced with the molten polyamide moulding composition according to one of the claims 7 to 13 with a light transmission of at least 75% measured according to ASTM 1003 at 2 mm thickness of the moulded part, characterized in that the transmission of said moulded parts for light with a wavelength of 400 nm at 2 mm thickness of the moulded part is less than 20%.
  15. Plastic moulded parts according to claim 14, characterized in that the transmission of these moulded parts for light with a wavelength of 400 nm is less than 10%.
  16. Plastic moulded parts according to claim 14, characterized in that the transmission of these moulded parts for light with a wavelength 400 nm is less than 5%.
  17. Plastic moulded parts according to claim 14, characterized in that the transmission of these moulded parts for light with a wavelength of 400 nm is less than 1%.
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AU2008202150A AU2008202150B2 (en) 2007-05-16 2008-05-15 Use of UV absorbers in the production of transparent polyamide molded parts
JP2008128547A JP5241318B2 (en) 2007-05-16 2008-05-15 Use of UV absorbers in the production of transparent polyamide moldings
KR1020080045625A KR101521298B1 (en) 2007-05-16 2008-05-16 Use of uv absorbers in the production of transparent polyamide molded parts
CN2008102103276A CN101328313B (en) 2007-05-16 2008-05-16 Use of UV absorbers in the production of transparent polyamide molded parts
US12/122,468 US8138243B2 (en) 2007-05-16 2008-05-16 Use of UV absorbers in the production of transparent polyamide molded parts
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